Passive micro-vessel and sensor

ABSTRACT

An electrically passive device and method for in-situ acoustic emission, and/or releasing, sampling and/or measuring of a fluid or various material(s) is provided. The device may provide a robust timing mechanism to release, sample and/or perform measurements on a predefined schedule, and, in various embodiments, emits an acoustic signal sequence(s) that may be used for triangulation of the device position within, for example, a hydrocarbon reservoir or a living body.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/871,383, filed Jan. 15, 2018, entitled “Passive Micro-vessel andSensor,” which in turn is a continuation in part of U.S. applicationSer. No. 14/244,292, filed Apr. 3, 2014, entitled “Passive Micro-vesseland Sensor,” which in turn is a continuation in part of U.S. applicationSer. No. 13/760,879, filed Feb. 6, 2013, entitled “Passive Micro-vesseland Sensor,” which in turn is a continuation in part of U.S. applicationSer. No. 13/025,467, filed Feb. 11, 2011, entitled “Passive Micro-vesseland Sensor,” which in turn claims priority from U.S. provisional patentapplication Ser. No. 61/337,998 filed Feb. 12, 2010, entitled “PassiveMicro-vessel and Sensor.” Each of the above-described applications ishereby incorporated herein by reference, in its entirety.

TECHNICAL FIELD

The present invention generally relates to an electrically passivedevice capable of communicating its position by acoustic emission atspecific time intervals, and/or of retrieving and/or sensing/and/ordetermining characteristics of fluid samples at, for example, specifictime intervals, and/or of time-release of particles, chemical products,or pharmaceutical products. More particular embodiments of the presentinvention relate, for example, to an electrically passive vessel foracquiring samples or releasing various particle/products in a subsurfaceformation (such as a geological or marine formation) or a living body,with the optional capability of providing measurements on the sample,and/or communicating its position via acoustic emissions.

BACKGROUND ART

Obtaining and analyzing samples of fluid from subsurface reservoirformations is often conducted during oil and gas exploration. Suchoperations are hindered by the harsh subterranean environment specificto oilfields, including high temperature and pressure (HPHT), corrosivefluids, and severely constrained geometry. The difficulty in acquiringand performing measurements on fluidic samples in such an environmentare further complicated by use of electronic sensors that typicallyrequire power, monitoring and/or telemetry.

Several oil-field related operations, such as fracturing a geologicalformation, would greatly benefit from the capability of producing a mapof the subterranean fracture geometry, and of the fracture evolution intime. Such capability does not currently exist. A similar need existsfor a technology which can be used in monitoring and performing fractureanalysis of subterranean carbon dioxide sequestration reservoirs.

Measurements of fluid properties and composition from an oil well aredifficult to perform in the oilfield environment. The capability toinject very small sensing devices far into a geological formation by useof a Proppant or similar means of sensor transport, and to be able todetermine their position and the precise moment when they perform ameasurement or acquire a sample would greatly benefit the industry.

Measurements need to be performed in other types of situations, wherethe deployment of active sensing systems with on-board electronics anddata transmission capabilities may either be impossible due toenvironmental issues (for example temperatures and pressures that aretoo high) or may prove to be too expensive to justify economically.Typical examples involve measurements within aquifers, potable waterwells, or in a submarine environment. Such an environment may be a lake,or a sea or ocean. Still further environments include where or whenthere is a lack of power, such as in remote areas of the world.

The capability to perform viscosity measurements on fluid samples isextremely important in a variety of industries: chemical engineering,food industry, oilfield, to name a few. Usually this is accomplishedusing large laboratory instruments such as capillary viscometers andrheometers, or by using portable lighter weight instruments. In mostcases, these instruments are operated using electrical power, andrequire sample manipulations that are difficult to automate. In someenvironments such instruments may be impractical due to their size (suchas in difficult to reach areas, or within downhole oilfield tools), maybe dangerous due to their electrical operation (inside explosiveenvironments such as refinery facilities and tanks, near oil and gaswells), may be incompatible with the shocks or vibrations (within an oilwell), or may be simply difficult to adapt. In this case new types ofviscosity measurements need to be devised that avoid suchinconveniences.

Samples often need to be acquired in explosive atmospheres (ATEXenvironments) such as inside refinery tanks (to determine the fluidquality and stratification), within refineries or gas plants or otherfacilities dealing with explosive environments. In such situations thesampling equipment should not pose a risk of generating an explosion, aswould be the case if an electrical spark were created. All-mechanicalsystems that are ATEX-certified are currently used in the industry toperform this type of sampling.

Furthermore, samples may need to be acquired from fluids that are athigh pressure, such as in a chemical factory, a refinery, inside an oilwell, or at high depth within the ocean. When pressure is lowered, suchsamples may change (or degrade) by undergoing a thermodynamic phasetransition leading to phase separation (i.e. gas may separate from oil,or asphaltenes may precipitate from heavy oil), in a possiblyirreversible manner. Sample containers in this case may need to befilled slowly, at controlled inflow into the sample vial or chamber, inorder to preserve the thermodynamic equilibrium and prevent, forexample, a pressure shock that may lead to phase separation or otherirreversible changes in the sample constituency. Such samples may alsoneed to be maintained at high-pressure conditions subsequent to sampleacquisition (for example during sample tool retrieval, or duringtransportation to a remote laboratory), to prevent sample degradationand maintain the sample characteristics unchanged.

Additionally, samples are often required in environments that poseobjective risks and dangers, or that are physically remote, or wherefrequent sampling using manual devices may prove impractical: sites ofnuclear disasters, military battlegrounds, biohazard or chemical hazardareas, terrorist attack sites, remote natural resources such as riversand lakes, coastal waters and other offshore locations, deep water andsub-sea environments. In such cases, robotic equipment may need to bedeployed, and the capability to take and analyze such samples mayprovide important information that cannot be acquired using the on-boardin-line sensors present on such equipment. Such equipment may consist ofautonomous or remotely-operated vehicles or robots; remotely-operatedunderwater vehicles; autonomous underwater vehicles such asbuoyancy-driven gliders and wave gliders; airborne or ground drones;other type of robotic equipment.

Samples often need to be acquired and analyzed to detect trace levels ofcertain contaminants that may be too dilute to enable direct detection.Sample pre-concentration may be required in such cases, by methods suchas filtration using mechanical filters, polymeric filters, fiber glassfilters, affinity columns, solid phase extraction columns, gaschromatography pre-concentration tubes and columns, or other types ofmaterial showing particular affinity for the contaminant, and possiblyincluded in porous or packed form. Particular care needs to be takenwhen acquiring such samples to prevent scavenging of the sample by, orits adsorption to, the materials of the sampling vial or chamber, or ofthe transport tubes. The filter material may need to be backflushed,often with a different solution, to remove filter cake buildup and togenerate a pre-concentrated sample that may need to be stored into aseparate vial or container for transport, storage, or for furthermanipulation and/or analysis. Alternatively, the filter itself may beretrieved and analyzed, after applying an optional extraction protocol,using laboratory equipment such as gas chromatography, high precisionliquid chromatography (HPLC), mass spectroscopy, gamma ray spectroscopy,or other analytical chemistry, biochemical, biological, or nuclearequipment, and possibly after solvent or thermal desorption.

Often there is a need to perform a chemical or biochemical reaction onthe acquired sample, by bringing it in contact with a known quantity ofchemical or biochemical reagent that will lead to a property change as aconsequence of the reaction. The chemical or biochemical reagent may bepresent as a liquid, solid, powder, gel, gas, emulsion or foam, and itmay be attached to, or immobilized on, a solid substrate such as thewalls of a vial, a strip of metal, tissue, plastic, paper (as is thecase of colorimetric test strips). The reagent may be lyophilized.Often, the (bio)chemical reaction results in color change, which can bedetected optically by spectrophotometric absorbance or by colorimetry.Other times direct fluorescence of the sample, or the presence of afluorescent byproduct, can be detected by fluorescence measurements.Many other properties of the sample may be measured such as (withoutlimitation) optical absorbance, chemiluminescence, color, turbidity,fluorescence intensity, index of refraction, conductivity, density,viscosity. In some cases the usage of a microplate with multiple wellsmay be necessary to prepare a sample and perform measurements on it.

Certain chemical or biochemical sample preparation protocols may requiremore complex sample manipulations, such as reaction with a firstreagent, waiting for an incubation or reaction time, and then bringingthe sample in contact with a second reagent. This sequence may need tobe repeated several times.

For pollution monitoring, often samples are not acquired instantaneouslybut rather over longer periods of time. The rate of sample intake may beproportional to flow velocity in the body of water being sampled. Thistechnique provides “integrated” water samples, which allow in somecircumstances to determine the average pollution of the body of waterover a period of time, rather than instantaneous pollution.

In certain applications, the moment when a sample needs to be acquiredmay not be known in advance, so that a pre-programmed sampling sequencemay not be appropriate. In this case, individual control of the momentwhen each sample is performed may be required. For example, samples mayneed to be acquired in the aftermath of an unforeseen accident, or asdirected by an external signal.

In some cases, there may be a need to acquire a larger number of samplesthan the capabilities of a single sampling device. In this case,multiple sampling devices may need to be used in a “daisy chainconfiguration”, in such a way that once a device acquires its maximumnumber of samples, it automatically triggers the next device that willtake over the sampling tasks. Using this approach, the total number ofsamples that can be acquired is not limited by the capabilities of anindividual device.

Often there is a need for injecting, or liberating, small particles orsmall amounts of chemicals at predefined times into a remoteenvironment, or into an environment which is difficult to access. Suchsmall particles or chemicals may be used as tracers, may participate inchemical reactions, or may be used as pharmaceuticals. Exemplaryenvironments where such particles, chemicals, or pharmaceuticals may beinjected include without limitation oil and water reservoirs,pre-existing or induced fractures within such reservoirs or within othergeological formations, oil, water and/or gas wells, water bodies such aslakes, rivers and oceans, or a human body. It may be desired that suchparticles or chemicals react in an aggressive way with the fluid presentin the remote environment, for example by producing an explosion orproducing a rapid release of energy

Monitoring of hazardous waste disposal reservoirs and of adjacentaquifers for contamination mapping and leaching is also a very importantdomain, where the need for miniaturized and economical sensing solutionsis prominent.

Unintended leaks, spills or discharges occur frequently aroundindustrial sites, and may affect environments such as the deep ocean(off-shore environment), a river, a lake, an estuary, the coastal water,or the atmosphere. In the case of an event concerning an unintendeddischarge, leak, nuclear or chemical spill from an industrial site orother facility, there is an inherent desire within the industry tounderstand the impacts of that event on the environment. In addition, itwould be desirable to be able to gather accurate data concerning thedistribution and movement of the pollution over time as it passesthrough the environment.

There are many factors that may affect the complex interaction of a leakinto a marine environment, including ocean currents, wind, waves,thermoclines, buoyancy, pressure, formation of gas hydrates and phasetransitions just to name a few. In order to make the best possiblepredictions using 3 dimensional models (in space) and 4 dimensionalmodels (over time) as an off-shore leak progresses, real data points arerequired to be entered into the models. Samples taken at differentpoints and different times around the spill area are a valuable methodfor determining the progression of a spill through the environment.However, technology today is very limited in terms of deployment andability to acquire a significant number of samples at multiple depthpoints, at multiple radial points from the source and at multiple pointsin time. Sample acquisition systems may need to be deployed in a waythat is non-intrusive to the normal operations in and around theindustrial facility (which may be a drilling rig, an off-shore platform,a ship, a tanker, a pipe etc.), both on the ocean surface and in thesubsea. In the early hours and days after an event occurs, resources arenormally dedicated to critical tasks other than environmental monitoringor sampling. Additionally, in most cases, the sampling capability isalso not located at the industrial site, but more likely on-shore andmay take days for the equipment to reach the offshore facility. There isa need for a system that is put in place around an industrial facilityas a precautionary measure at an early stage in the project.Furthermore, the position of the system should be accurately determinedat the time of installation. Acquired samples and subsea systems alsoneed to be easily retrievable by an ocean vessel at the ocean surface.

In the case that a sampling system is placed in the marine environmentfor an extended period of time, biofouling and biogrowth tends todevelop on the system, including at the sampling intake ports.Similarly, in a deep-water environment near hydrocarbon productionfacilities, there is a risk of methane hydrate formation. This providesa serious risk of blockage, contamination and/or unrepresentativesampling. Thus the need for a system that is able to not only remain instandby mode ready for deployment, but also be in a protectedenvironment that rejects any biogrowth or methane hydrate from formingduring the standby period.

Often there are cases where a sampling unit or an array of samplingunits needs to be deployed in a non-static environment, such as whenthere is a natural ocean current or wave motion due to winds, or othermovement within the water column. This movement may, or may not, be inthe same direction at all times, may not be predictable, and may causethe sampling unit or string of units to be in a position that is notvertically above the original anchoring point, or vertically below abuoy or similar water-surface mooring point. Consequently, this maycause error in the assumed position data associated with the samplingunit or array.

Currently, sample loading and measurement protocols for microbiologicalmeasurements often need to be performed manually, requiring specializedlabor and equipment and incurring significant costs. In addition, suchmeasurements require the collection of a representative sample from theenvironment being monitored (that may be a lake, a river, a pool, areservoir, a groundwater well, an estuary, coastal water, drinkingwater, wastewater on any other water source), and transportation to aspecialized laboratory where the measurements are performed. Thisprotocol provides a risk of human error in the sampling and/ortransportation procedure, leading to an unrepresentative sample beingcollected, or to sample contamination and/or degradation duringtransport. There is a need therefore for a device that is capable toperform the sampling and analysis operation in-situ, in a repeatable andreproducible manner, thus bypassing certain human intervention stepsthat are prone to creating errors.

In certain applications, there is a need for very precisely controllingthe moment when each sample is being acquired in a series of samplingoperations. These moments may depend of certain external events thatcannot be predicted or anticipated at sampler installation, andtherefore the sample acquisition moments cannot be pre-programmed in thesampler design.

A sampler may also require a means to actuate the sampling mechanism ina rapid manner upon the receipt of the signal to sample followingexternal trigger activation, such as in the seconds or millisecondsfollowing the receipt of the signal. Furthermore, a sampling device mayrequire means for confirming that a sample was actually acquired, forrecording the exact time when each sample was acquired (also known as atimestamp), as well as a certain amount of information corresponding tothe sampling process, such as the total duration over which a samplecontainer was filled, the total amount that was sampled etc.

It is important that any timing mechanism used to trigger theacquisition of a fluid sample be accurate, however in certainapplications such timing may not prove accurate enough. For example,timing errors in fluidic clocks may occur due to small manufacturingimperfections that may change the overall timing of the sampleacquisition. For example, a ten percent relative error in the volume ofa timing cavity will result in a ten percent relative error in thetiming of that particular sample acquisition. If the overall timing wasdesigned to be ten hours, a ten percent error will introduce a one-hourabsolute error in the timing, so the sample may be acquired an hourprior to, or an hour later than the scheduled time.

Such timing errors provided by fluidic clocks may become particularlyproblematic when a series of samples needs to be acquired in sequence.For example, assume one sample needs to be acquired every hour for aperiod of twenty four hours. Twenty four sampling devices are deployedat t=0, device numbered n (1<n<24) having a time constant of n hoursprior to triggering the acquisition of its corresponding sample. Ifthere is a ten percent error in the fluidic clock of each samplingdevice, that means that it is likely that the order of the samplingevents will be disturbed. For example, the 10th device may acquire itssample at t=11 h, and the 11th device at t=10 h, thus they will be outof order.

SUMMARY OF THE INVENTION

In accordance with an embodiment of the invention, a system may includeone or more sampling devices, each device including at least onesampling mechanism. Each sampling mechanism includes a timing diaphragm,a timing cavity, a mechanical structure and an isolated cavity. Each ofthese parts may be built on a single physical substrate, or may beseparate parts that are connected together by tubes, pipes, o-ring orgasket joints, or other types of mechanical or fluidic fixtures known tothe person skilled in the art. Each sampling mechanism further includesa conduit that may be a microfluidic channel or a capillary tube, andthat may have a predefined geometry. Upon applying pressure to a timingfluid within the conduit, said timing fluid being a liquid or a gas, thetiming fluid advances within the microfluidic channel at a speed, forexample, that may be dictated by the applied pressure, the predefinedchannel geometry and/or known timing fluid properties. Upon reaching thetiming cavity and filling it after a timing interval, the timing fluidapplies pressure to the timing diaphragm which ruptures and/or collapsesthe mechanical structure, thus allowing the external fluid to enter theisolated cavity, which may then further lead to a sampling chamber. Theisolated cavity and the sampling chamber may be part of the sameassembly as the sampling mechanisms, or they may be separate parts thatare connected using some form of fluidic or mechanical fixture known tothe person skilled in the art. The timing diaphragm's movement may bepartially restricted by using any type of mechanical system known to theperson skilled in the art, such as, without limitation, a mechanicalstop, a spring, a boss, a support or any combination thereof. Suchrestriction may protect the timing diaphragm from breaking under theeffect of one, or both, of timing fluid pressure and external fluidpressure.

In accordance with related embodiments of the invention, the samplingmechanism may include, in the place of the timing diaphragm, a pistonthat may be, for example, configured to move within the isolated cavityupon applying pressure to one side of the piston. The sampling mechanismmay further include a conduit that may be a microfluidic channel or acapillary tube, and that may have a predefined geometry. Upon applyingpressure to a timing fluid (liquid or gas) within the conduit, saidtiming fluid advances within the microfluidic channel at a speed, forexample, that may be dictated by the applied pressure, the predefinedchannel geometry and known timing fluid properties. Upon reaching thetiming cavity and filling it after a timing interval, the timing fluidapplies pressure to one side of the piston, which advances within apiston cavity and, upon reaching the mechanical structure, appliesmechanical stress to the mechanical structure causing it to ruptureand/or collapse, thus allowing the external fluid to enter the isolatedcavity, which may then further lead to a sampling chamber. The pistonmay include a piercing structure, which may, for example, be aprotrusion that concentrates the stress applied to the mechanicalstructure. Such protrusion may be a needle, a pin, a raised boss, or anyother type of structure known in the art, and it may be separate fromthe piston or an integral part of it. The isolated cavity and thesampling chamber may be part of the same assembly as the samplingmechanisms, or they may be separate parts that are connected using someform of fluidic or mechanical fixture known to the person skilled in theart.

In accordance with further related embodiments of the invention, thecombination of channel geometry, timing cavity volume, applied timingfluid pressure and timing fluid properties may be chosen such that thetiming fluid advances within the channel at a speed that will assurefilling of the timing cavity in a time interval that falls within a timerange of interest for the given application. Said time range of interestmay be, without limitation, depending on the given application, lessthan 100 milliseconds, between 0.1 milliseconds and 10 milliseconds, orbetween 10 millisecond and 1 second, or between 1 seconds and 100seconds, or of longer or shorter duration. That range of interest mayextend to many days, weeks and months.

In accordance with related embodiments of the invention, the mechanicalstructure may be made of an inorganic material, a non-polymericmaterial, silicon, glass, ceramic and combinations thereof. Themechanical structure may be insoluble in water, bodily fluids, oil,crude oil, oil field fluid, salt water, sea water and combinationsthereof. The conduit may be, without limitation, initially at leastpartially filled the timing fluid, or in other embodiments, the timingfluid may be the external fluid that enters from the isolated cavity.The device may include a plurality of sampling mechanisms. At least onesampling mechanism may have a conduit having different dimensions thananother sampling mechanism, and/or a timing cavity of different volumefrom another timing mechanism, such that the timing fluid of thedifferent sampling mechanisms reach and fill their associated timingcavities at different times. The sampling mechanism may include a checkvalve that allows flow of fluid into the sampling chamber but preventsflow of fluid out of the sampling chamber. The device may release aweight upon sample acquisition so as to maintain a constant mass and notmodify its submerged weight and buoyancy.

In accordance with related embodiments of the invention, the samplingchamber may include a compressed spring and a piston, one side of thepiston in contact with the sampling chamber and the other side incontact with the external fluid, such that prior to sampling beinginitiated the spring is compressed by the piston due to external fluidpressure being applied to the piston, and upon sampling being initiated,the hydrostatic pressure on both sides of the piston equalizes and theelastic force of the spring displaces the piston, thus acquiring asample at controlled speed and with minimal change to the overallsubmerged weight and buoyancy of the device. The travel of the pistonmay be restricted due to the presence of a mechanical fixture such as astop or a ridge.

In accordance with further related embodiments of the invention, aconduit, such as a microfluidic channel or capillary tube, may beimplemented between the mechanical structure and the sampling chamber,or within the sample chamber itself, such that upon the collapse ofrupture of the mechanical structure, the sample enters the samplingchamber at a low flow rate controlled by the conduit, and fills thesampling chamber over a controlled period of time.

In accordance with yet further related embodiments of the invention, thedevice may force the sample to come in contact, upon or prior toentering the sampling chamber, with a filter that may be one of thefollowing (without limitation): a mechanical filter, a solid phaseextraction column, a hydrocarbon filter, a gas chromatographypreconcentrator, a filter to collect and concentrate radioactivematerial, a biological filter, an absorbent medium, a scavenging medium,a hydrophobic material, and hydrophilic material, or any combinationthereof. The filters may, optionally, be later retrieved and analyzed,to provide time-series data concerning the contaminant of interest atthe location of the device.

In accordance with further related embodiments of the invention, anacoustic signal may be emitted from the device upon the mechanicalstructure rupturing and/or collapsing. The isolated cavity and themechanical structure may be shaped to emit a predetermined acousticsignal upon the mechanical structure collapsing. The device may includea plurality of sampling mechanisms, each sampling mechanism having anacoustic signature upon collapse of its associated mechanical structure,wherein the acoustic signatures of the sampling mechanisms vary. Thedevice may include a plurality of sampling mechanisms, wherein at leastone sampling mechanism has a conduit, such as a microfluidic channel orcapillary tube, having different dimensions than another samplingmechanism, such that the timing fluid of the different samplingmechanisms reach their associated cavities at different times so as toproduce multiple acoustic events that occur at different times. Thesampling chamber may include a sensor element for performing a detectionand/or a measurement on the fluid. The sensor element may include, forexample, a material that interacts with the fluid and/or electrodesallowing an electrochemical measurement to be performed on the fluidsample. The device may be electrically passive. The isolated cavity mayinclude a micro-particle, a nano-particle, a chemical product, and/or apharmaceutical product, which is released into the environment after thecollapse and/or rupture of the mechanical structure separating theisolated cavity from the exterior environment. The chemical in questionmay react in an aggressive way with the environment, such as bygenerating an explosion or some other form of rapid energy release. Thedevice may include a filter and/or a sieve to retain broken mechanicalstructure parts from entering at least one of the isolated cavity andthe environment surrounding the device.

In accordance with still further related embodiments of the invention,the system may include a sampling chamber for receiving fluid from theisolated cavity, the sampling chamber partially pre-filled with aculture medium that allows select classes of microorganisms to developand grow, such that once a sample is acquired, the sample comes incontact with the culture medium. If the sample is contaminated with theselect classes of microorganisms, these will multiply, over anincubation period, due to the presence of the culture medium. Thesampling chamber may further include a temperature control mechanismthat ensures that the sample temperature is maintained within a rangethat is optimal for sample incubation. The sampling chamber may furtherinclude chemical and/or biological reagents allowing the detection ofthe presence and/or of the quantity of said microorganisms. Suchdetection may be performed optically, for example by monitoring thecolor of the sample via an optical absorption measurement, or bymonitoring its fluorescence.

In accordance with yet further related embodiments of the invention,communications may be provided with a sampling device or a system ofmultiple sampling devices by means of a wired or wireless link, so as toremotely trigger the beginning of one or multiple sample acquisitionoperations. Examples of such means of communication include amechanical, acoustical, electrical or electromagnetic wired or wirelesslink, for example, and without limitation, a mechanical cable or lever,a serial communication cable, a parallel communication cable, anelectrical triggering cable, an electromagnetic wave using a mobiletelephony network or a radio frequency or satellite connection, apressure wave such as an acoustic or sound wave using an acoustic module(such as sonar and/or a hydrophone, a speaker and a microphone, orsimilar), a wi-fi or Bluetooth connection, an optical signal such as alaser signal, or any other form of acoustic, electrical,electromagnetic, acoustic or mechanical communication means and/ortrigger known to the person skilled in the art.

In accordance with another related embodiment of this invention, asampling device may be provided that may be remotely triggered. Thesampling device may include a passive timing mechanism with a short timeconstant that allows, such that upon receipt of the trigger signal, asample can be acquired within a relatively short time interval. Such apassive timing mechanism may combine appropriately-sized timing cavityand timing channel, a timing fluid of appropriate viscosity and a timingfluid pressure of appropriate magnitude, to result in a short timinginterval prior to breaking the associated mechanical structure. Such atime interval may be less than 100 ms. In various applications, the timeinterval may range from 0.1 ms to 10 ms or 10 ms to 1 s In other timeapplications the required timing may be significantly longer.

In accordance with still further related embodiments of the invention, amonitoring system is provided for monitoring the sampling acquisitionprocess, and, without limitation, to record a time-stamp, allowingprecise recording of sample acquisition time by the sampling device.

The monitoring may be achieved by using a pressure measurement performedinside the sample chamber, as triggered by a processor or at predefinedtimes, preferably in a periodic manner. Optionally, a second pressuremeasurement may be performed to monitor the pressure of the externalmedium. Pressure sensors may be in communication with a processor thatcan process their data and record it in a memory module, and/or transmitit to an external data recording system using a wired or wirelessconnection. The timestamp of the sample acquisition (t_(samp)) may beinferred by monitoring the sample chamber pressure sensor for asignificant deviation from the initial pressure in the sample chamber(p_(ini)). In various embodiments, the sample chamber may include apressure switch that activates once the pressure inside the chamberincreases past a given threshold. The moment of the activation of thepressure switch corresponds to the timestamp of the sample, t_(samp).This timestamp may be recorded by the monitoring system. In variousembodiments of the invention, the pressure curve recorded from thepressure sensor inside the sample chamber may be used to determine asample fill-up duration Δt by recording the time t_(fill) when pressurestabilizes within the sample chamber, and subtracting from this valuethe time corresponding to beginning of the sample acquisition t_(samp):Δt=t_(fill)−t_(samp). In various embodiments, the value p_(ini) of theinitial pressure in the sample chamber prior to sample acquisition, thevalue p_(fin) at which pressure has stabilized in the sample chamberafter the sample acquisition, and p_(ext), the pressure measured by thesensor monitoring the pressure of the external medium, may be used todetermine the total volume of the sample acquired.

In accordance with further related embodiment of the invention, thesample chamber may include optical elements for monitoring andperforming a measurement of, without limitation, turbidity, absorbance,color, transmittance, autofluorescence, or fluorescence, or anycombinations thereof. The sample chamber may incorporate certain opticalcomponents, either inside the sample container or in its proximity, inorder to assure that the light travels across or around, or otherwiseinteracts with the sample in an optimal way. The sample chamber may beequipped with, for example: one or several optical windows allowing anoptical measurement to be performed on the sample contained within thesample chamber, one or multiple light sources, optical detectors,sensors or recording devices (such as, without limitation cameras,individual photodiodes or arrays thereof, other types of opticalsensors, phototransistors, avalanche photodiodes, photomultipliers),mechanical positioning assemblies, fibers, diaphragms, mirrors,optically absorbing surfaces, optical filters of all kinds (such as,without limitation neutral filters, band-pass filters, low-pass filters,high-pass filters, dichroic filters) or any other type of opticalcomponent or device known to the person skilled in the art, or anycombination or configuration thereof.

In another embodiment of the invention, the exact time of the sampleacquisition (its timestamp) is measured optically, by monitoring achange in the optical properties of the sample chamber. Said monitoringmay include an absorbance measurement performed on the acquired sampleat a wavelength where the sample fluid absorbs light (such that themeasured absorbance will be higher after sample acquisition than priorto it). Alternatively, the monitoring may involve an optical signal (orlack thereof) related to the deviation of the light path due to thechange in optical refraction index caused by the sample acquisitionwithin the sample chamber.

Any other type of measurement, optical or not, that is known to theperson skilled in the art, may be used to determine whether a sample hasbeen acquired within the sample chamber. This may include a conductivitymeasurement, a temperature measurement, an electrochemical measurement,an optical measurement, a physical measurement, a force measurement, adeflection measurement, a chemical measurement, a biological orbiochemical measurement, or any combination thereof.

In accordance with further related embodiments of the invention, apassive timing mechanism of improved precision is described, involving asampling device that includes multiple sampling mechanisms capable oftiming and performing the acquisition of multiple (n) samples in anelectrically-passive way, whereas the electrically-passive timingmechanism corresponding to sample i+1 is triggered at a time instantthat is related to the time of acquisition of sample i. Moreparticularly, at least one of the one or more devices includes a firstsampling mechanism and a second sampling mechanism, wherein the piercingof the mechanical structure and acquisition of a sample by the firstsampling mechanism acts as a trigger for activating the timing mechanismof the second sampling mechanism.

In accordance with yet further related embodiment of the invention, asampling device may include two sampling mechanisms such that there are,without limitation, two timing diaphragms (or, for example, twopistons), two connected timing cavities, two mechanical structures andtwo isolated cavities. The first mechanical structure separates anexternal fluid from the first isolated cavity. Each sampling mechanismfurther includes a conduit that may be a microfluidic channel or acapillary tube, and that may have a predefined geometry. Upon applyingpressure to a timing fluid within the conduit, said timing fluid being aliquid or a gas, the timing fluid advances within the microfluidicchannel at a speed, for example, that may be dictated by the appliedpressure, the predefined channel geometry and known timing fluidproperties. The timing fluid conduit is also connected, by a tube orsimilar fluidic connection, to the second mechanical structure. Uponreaching the connected timing cavities and filling them after a timinginterval, the timing fluid applies pressure to the two timing diaphragmssimultaneously, thus destroying their corresponding mechanicalstructures, e.g. by rupturing and/or collapsing them. The firstmechanical structure, once destroyed, allows a sample of the externalfluid to be acquired by enabling the external fluid to enter theisolated cavity, which may then further lead to a sampling chamber. Thesecond mechanical structure, once destroyed, opens a passage for thetiming fluid to enter the timing fluid conduit of a subsequent samplingmechanism, thus acting as an effective trigger for timing theacquisition of the next sample.

In accordance with still further related embodiments, a tool mayincorporate the above-described device. The tool may have an interiorflow-line through which a sample fluid is capable of circulating and inwhich the one or more devices are positioned, wherein said sample fluidwhen circulating in the interior flow-line contacts the devices. Thetool may include a pad capable of being pushed into a formation wall toreceive fluid, and a pump for pumping formation fluid into the interiorflow-line. The tool may further include at least one microphone forreceiving acoustic emissions from the one or more devices. Othermicrophones may be located at different positions on the ground in thearea surrounding a well, or within wells drilled elsewhere in theformation. The tool may include a processor for performing atime-stamping of the received acoustic emissions and/or a determinationof device positioning. The tool may include a retrieval mechanism forretrieving the devices from an underground formation. The retrievalmechanism may include one of a pumping device and a suction device.

In accordance with still further related embodiments, theabove-described device may be injected from the surface into anunderground formation by pumping it along with a carrier fluid orproppant through a well. Monitoring of the acoustic emissions from thedevice may be performed using microphones placed in the injection well,in a well drilled elsewhere in the area, or on the ground. The devicemay be deployed in a pipe, a well, an engine, a hydrocarbon reservoir,an aquifer, a body of water, an oil field tool, a waste disposalreservoir, a proppant formulation and/or a living body.

In accordance with another embodiment of the invention, a device forsampling a fluid includes at least one sampling mechanism, which may beelectrically passive. Each sampling mechanism includes an isolatedcavity, a mechanical structure and a microfluidic timing mechanism. Uponthe microfluidic timing mechanism being subject to pressure, themechanical structure collapses and/or punctures and/or ruptures after atime delay, allowing external fluid to enter the isolated cavity, whichmay then further lead to a sampling chamber.

In accordance with related embodiments of the invention, themicrofluidic timing mechanism may include a conduit that may be amicrofluidic channel or a capillary tube, and that may have a predefinedgeometry. Upon applying pressure to a timing fluid within the conduit,the timing fluid advances within the conduit at a speed, for example,that may be dictated by the predefined channel geometry and known timingfluid properties The microfluidic timing mechanism may include a timingcavity and a timing diaphragm, and wherein upon the timing fluidadvancing and reaching/filling the timing cavity, the timing fluidapplies pressure to expand the timing diaphragm, collapsing themechanical structure and thus allowing the external fluid to enter theisolated cavity. The sample cavity may include a sensor element forperforming a detection and/or a measurement on the fluid that enters thesample chamber. The isolated cavity may include a micro-particle, anano-particle, a chemical product, and/or a pharmaceutical product,which is released into the environment after the collapse and/or ruptureof the mechanical structure separating the isolated cavity from theexterior environment. The device may emit a predetermined acousticsignal upon collapse of the mechanical structure, or upon the reactionof the content of the cavity with the external environment. Suchreaction may be designed to be aggressive, such as an explosion. Thedevice may include a filter and/or a sieve to retain broken mechanicalstructure parts from entering at least one of the isolated cavity andthe environment surrounding the device.

In accordance with further related embodiments of the invention, asystem includes one or more of the above-described devices. The systemfurther includes at least one microphone, geophone, seismometer,accelerometer and/or other type of sensor for receiving acousticemissions from the one or more devices. A processor may timestamp thereceived acoustic emissions and/or determine a position of the one ormore devices based, at least in part, on the received acousticemissions. The device may be deployed within a pipe, a well, an engine,a hydrocarbon reservoir, an aquifer, a body of water, an oil field tool,a waste disposal reservoir, a proppant formulation and/or a living body.

In accordance with another embodiment of the invention, a system forsampling a fluid includes at least one device, which may be electricallypassive. Each device includes a mechanical structure, and a microfluidictiming mechanism that, upon the microfluidic timing mechanism beingsubjected to pressure, collapses the mechanical structure after a timedelay. Upon collapse the mechanical structure emits an acousticsignature, and may allow fluid to enter a sample chamber. The systemfurther includes a microphone for receiving the acoustic signature, anda processor operatively coupled to the microphone. The processor may,for example, extract the position of the device based, at least in part,on the received acoustic signature.

In accordance with another embodiment of the invention, a methodincludes deploying a device in a fluid. An acoustic cavity within thedevice is opened to the fluid at a time determined by an electricallypassive timing mechanism. The device emits an acoustic signature whenthe cavity is opened.

In accordance with related embodiments of the invention, a sample may beacquired upon opening of the cavity. The acoustic signature may bedetected using, at least in part, one or more microphones, geophone,accelerometer and/or other type of sensor. The detected acousticsignature may be time-stamped. The position of the device may beextracted from the detected acoustic signature using, withoutlimitation, triangulation, compressional signal processing, and/or shearsignal processing. The device may be deployed in a geological formationor a formation fracture. For example, the device may be pumped into thegeological formation. Deploying the device may include using the devicein a hydraulic fracturing operation. The device may be deployed in afluid within a pipe, a fluid within a well, a fluid within an engine, ahydrocarbon reservoir, an aquifer, a body of water, a fluid within anoil field tool, a waste disposal reservoir, a proppant formulationand/or a living body.

In accordance with further related embodiments of the invention, thetiming mechanism may include a timing diaphragm or a piston, a timingcavity, and a conduit that may be a microfluidic channel or a capillarytube, and that may have a predefined geometry. Upon applying pressure toa timing fluid within the conduit, the timing fluid advances within themicrofluidic channel at a speed, for example, that may be dictated bythe predefined channel geometry and known timing fluid properties. Uponreaching and filling the timing cavity after a timing interval, thetiming fluid applies pressure to the timing diaphragm or piston whichopens the acoustic cavity within the device to the external fluid. Theconduit may be, without limitation, initially at least partially filledwith the timing fluid. In other embodiments, the timing fluid may be,without limitation, the external fluid that enters from the isolatedcavity.

In accordance with still further embodiments of the invention, at leastone of a micro-particle, a nano-particle, a chemical product, amaterial, and a pharmaceutical product may be stored within the deviceand released into the external fluid upon collapse of the acousticcavity. The particles, product or material that is released may reactaggressively with the environment, thus generating a further acousticsignal. A sample of the external fluid may be stored within the deviceupon collapse of the acoustic cavity.

In accordance with another embodiment of the invention, a deviceincludes an isolated cavity that is initially inaccessible to anexterior environment, and an electrically passive timing mechanism. Amechanical structure separates the isolated cavity from the exteriorenvironment, such that at the end of a timing interval the timingmechanism acts on the mechanical structure in a way that ruptures and/orcollapses it, thus bringing the isolated cavity in contact with theexterior environment.

In accordance with a related embodiment of the invention, the devicetiming mechanism may include a timing membrane or piston, a timingcavity, and a conduit that may be a microfluidic channel or a capillarytube, and that may have a predefined geometry. Upon applying pressure toa timing fluid within the conduit, the timing fluid advances within themicrofluidic channel at a speed, for example, that may be dictated bythe predefined channel geometry and known timing fluid properties Uponreaching and filling the timing cavity after a timing interval thetiming fluid applies pressure to the timing diaphragm or piston whichcollapses the mechanical structure, thus allowing external fluid toenter the isolated cavity. The conduit may be, without limitation,initially at least partially filled with the timing fluid. In otherembodiments, the timing fluid may be, without limitation, the externalfluid that enters from the isolated cavity.

In accordance with further related embodiments of the invention, thedevice may include an external device for applying pressure to thetiming fluid. The mechanical structure may be an isolation membraneand/or diaphragm. The isolated cavity may include a sampling chamber,the sampling chamber including a check valve that allows flow of fluidinto the sampling chamber but prevents flow of fluid out of the samplingchamber. An acoustic signal may be emitted from the device upon ruptureof the mechanical structure. The isolated cavity and the mechanicalstructure may be shaped to emit a predetermined acoustic signal upon themechanical structure collapsing. The isolated cavity may include asensor element for performing a detection and/or a measurement on thefluid. The sensor element may include a material that interacts, such aschemically, with the fluid. The sensor element may include an electrode,allowing, for example, an electrochemical measurement to be performed onthe fluid sample. The sensor element may be a Micro-Electro-MechanicalSystems (MEMS) device that may be microfabricated.

In accordance with further embodiments of the invention, the externaldevice for applying pressure to the timing fluid may include a devicesuch as an accumulator, that incorporates a piston or a membrane, towhich a force is transmitted using any means known in the art, such as acushion of compressed gas, or a mechanical spring, or contact with areservoir of fluid that is itself pressurized. The said reservoir offluid may be the external fluid itself. Alternatively, the externaldevice for applying pressure to the timing fluid may include a flexiblebag, itself placed within a pressurized reservoir, such as the pressureof the reservoir is transmitted to the timing fluid. Such a reservoirmay be pressurized by any means known in the art, such as by using acompressed gas cushion, or a mechanical spring mechanism, or contactwith a reservoir of fluid that is itself pressurized. The said reservoirof fluid may be the external fluid itself.

In accordance with further related embodiments of the invention, twosystems, each including multiple sampling devices that are timed such asto acquire the corresponding samples at different times, may have themechanical structure of the last sampling device of the first systemconnected to the timing fluid reservoir of the second system. At thesame time, the sampling cavity of the last sampling device of the firstsystem may be connected to the timing fluid channels of the seconddevice. In this configuration, the collapse or rupture of the mechanicalstructure of the last sampling device of the first system triggers thestart of the sampling using the second system, thus allowing the systemsto be connected in a daisy-chain configuration.

In accordance with yet further embodiments of the invention, theisolated cavity may include a micro-particle, a nano-particle, achemical product, and/or a pharmaceutical product, which is releasedinto the environment after the collapse and/or rupture of the mechanicalstructure separating the isolated cavity from the exterior environment.The device may include a filter and/or a sieve to retain brokenmechanical structure parts from entering at least one of the isolatedcavity and the environment surrounding the device.

In accordance with additional related embodiments of the invention, thedevice may include a plurality of isolated cavities, a plurality ofpassive timing mechanisms, and a plurality of mechanical structures. Atleast one of the passive timing mechanisms may have a timing intervaldifferent from the other timing mechanisms, such that the mechanicalstructures associated with the at least one passive timing mechanismruptures and/or collapses at a different time.

In accordance with still further related embodiments of the invention, asystem may include a plurality of the above-described devices, whereineach device has an acoustic signature upon collapse of its associatedmechanical structure, wherein the acoustic signatures of the devicesvary. A system may include a plurality of the above-described devices,wherein at least one device has a conduit having different dimensionsthan another device in the system, such that the timing fluid of thedifferent sampling mechanisms reach their associated cavities atdifferent times so as to produce multiple acoustic events that occur atdifferent times. A tool may incorporate one or more of theabove-described devices, the tool having an interior flow-line throughwhich a sample fluid is capable of circulating and in which the one ormore devices are positioned, wherein said sample fluid when circulatingin the interior flow-line contacts the devices. The tool may furtherinclude at least one microphone for receiving acoustic emissions fromthe one or more devices, and a processor for performing timestamping ofthe received acoustic emissions and/or determination of devicepositioning. A method using at least one of the above-described devicesmay include deploying the device within one of a pipe, a well, anengine, a hydrocarbon reservoir, an aquifer, a body of water, a wastedisposal reservoir, an oil field tool, a proppant formulation and aliving body.

In accordance with yet further related embodiments of the invention, asystem may include a plurality of the above-described devices, whereinthe system is incorporated into an underwater measurement system. Thesystem may be attached or otherwise embedded in a cable. The cable maybe further attached to a fixed buoy, or towed through a body of water bya ship or an underwater vehicle.

In accordance with another embodiment of the invention, a methodincludes deploying a device in an external fluid. A cavity is openedwithin the device to the external fluid, at a time determined by anelectrically passive timing mechanism. Upon the cavity opening, amicro-particle, a nano-particle, a chemical product, and/or apharmaceutical product is released from the cavity into the externalfluid, and/or a sample of the external fluid may be stored within thedevice. The particle or chemical or pharmaceutical product stored withinthe cavity may react in an aggressive or explosive way with the externalenvironment.

In accordance with related embodiments of the invention, the passivetiming mechanism may include a timing diaphragm or a piston, a timingcavity; a conduit that may be a microfluidic channel or a capillarytube, and that may have a predefined geometry. Upon applying pressure toa timing fluid within the conduit, the timing fluid advances within themicrofluidic channel at a speed, for example, that may be dictated bythe predefined channel geometry and known timing fluid properties. Uponreaching the timing cavity after a timing interval, the timing fluidapplies pressure to the timing diaphragm or piston which opens thecavity within the device to the external fluid. The conduit may be,without limitation, initially at least partially filled with the timingfluid. In other embodiments, the timing fluid may be, withoutlimitation, the external fluid that enters from the isolated cavity.

In accordance with further related embodiments of the invention,deploying the device may include pumping the device into a geologicalformation and/or a formation fracture. The device may be deployed in apipe, a well, an engine, a hydrocarbon reservoir, an aquifer, a body ofwater, an oil field tool, a waste disposal reservoir, a proppantformulation and/or a living body.

In accordance with still further embodiments of the invention, themethod may include emitting by the device an acoustic signature when thecavity is opened. The acoustic signature may be detected using, at leastin part, one or more microphone. A position of the device may beextracted from the detected acoustic signature using triangulation,compressional signal processing, and/or shear signal processing.

In accordance with another embodiment of the invention, a deviceincludes an electrically passive timing mechanism and a mechanicalstructure. At the end of a timing interval, the timing mechanismruptures the mechanical structure so as to emit an acoustic signal.

In accordance with related embodiments of the invention, the device mayinclude an isolated cavity, wherein the mechanical structure separatesthe isolated cavity from the exterior environment, and wherein rupturingthe mechanical structure brings the isolated cavity in contact with theexterior environment. The mechanical structure may be an isolationmembrane.

In accordance with further embodiments of the invention, the timingmechanism may include a timing diaphragm or a piston, a timing cavity,and a conduit that may be a microfluidic channel or a capillary tube,and that may have a predefined geometry. Upon applying pressure to atiming fluid within the conduit, the timing fluid advances within themicrofluidic channel at a speed, for example, that may be dictated bythe predefined channel geometry and known timing fluid properties. Uponreaching and filling the timing cavity, the timing fluid appliespressure to the timing diaphragm or piston, which ruptures and/orcollapses the mechanical structure, which thus may allow external fluidto enter the isolated cavity. The conduit may be, without limitation,initially at least partially filled with the timing fluid. In otherembodiments, the timing fluid may be, without limitation, the externalfluid that enters from the isolated cavity. The isolated cavity mayinclude a sampling chamber, the sampling chamber including a check valvethat allows flow of fluid into the sampling chamber but prevents flow offluid out of the sampling chamber. The sampling chamber may include asensor element for performing at least one of a detection and ameasurement on the fluid. The sensor element may include a material thatinteracts with the fluid. The sensor element may include electrodesallowing an electrochemical measurement to be performed on the fluidsample.

In accordance with further related embodiments of the invention, themechanical structure may be shaped to emit a predetermined acousticsignature upon rupturing. The device may be microfabricated.

In accordance with still further related embodiments of the invention, asystem includes a plurality of the above-described devices, wherein eachdevice has an acoustic signature upon rupture of its associatedmechanical structure, wherein the acoustic signatures of the devicesvary. The system may be incorporated into an underwater measurementsystem. The devices may be attached to a cable. The cable may be towedthrough a body of water by one of a ship and an underwater vehicle. Thedevice(s) may be used during a hydraulic fracturing operation.

In accordance with various embodiments of the invention, the timingfluid in the above-described embodiments may either be a Newtonian fluidof known viscosity or a non-Newtonian fluid of known rheology. A complexnon-Newtonian shear-thinning fluid may have a number of advantages,namely the fact that the non-Newtonian timing fluid will have a veryhigh viscosity at low shear stress (i.e. at low applied pressure), butthe viscosity will drop rapidly as the stress is increased. In variousembodiments of the invention, a complex non-Newtonian fluid may be usedas a timing fluid, resulting in a timing mechanism which only becomesactive once the ambient pressure has reached a certain threshold valueand providing additional versatility to the timing mechanism.

In accordance with another embodiment of the invention, a systemincludes one or more devices. Each device includes an isolated cavitythat is initially inaccessible to an external fluid and an electricallypassive timing mechanism. Each device further includes a mechanicalstructure that separates the isolated cavity from the exteriorenvironment, such that at the end of a timing interval the timingmechanism acts on the mechanical structure to rupture and/or collapsethe mechanical structure, thus bringing the isolated cavity in contactwith the external fluid.

In accordance with related embodiments of the invention, the mechanicalstructure may be made of an inorganic material, a non-polymericmaterial, silicon, glass, or a ceramic, or combinations thereof. Themechanical structure may be insoluble in a liquid, such as water, bodilyfluids, oil, crude oil, oil field fluid, salt water, or sea water, orcombinations thereof.

In accordance with further related embodiments of the invention, theisolated cavity may be in fluidic communication with a sampling chamber.A one-way check valve may be included between the isolated cavity andthe sampling chamber that allows fluid flow into the sampling chamber.The sampling chamber may include one or more chemical and/or biologicalreagents. The system may further include a filter for filtering fluidupon or prior to entering the sampling chamber. The filter may be amechanical filter, a solid phase extraction column, a hydrocarbonfilter, a gas chromatography preconcentrator, a packed column, a filterthat collects and concentrates radioactive material, a biologicalfilter, an absorbent medium, a scavenging medium, a hydrophobicmaterial, or a hydrophilic material, or a combination thereof.

In accordance with yet further related embodiments of the invention, thesampling chamber of a first device of the one or more devices mayinclude a piston and/or a flexible membrane that separates the samplingchamber into a first portion and a second portion, with the firstportion in fluidic communication with the isolated cavity. The secondportion may be in fluidic communication with an auxiliary chamber via aconduit, wherein the second portion is initially filled with a secondaryliquid, and wherein upon rupture and/or collapse of the mechanicalstructure, fluid from the external environment enters the samplingchamber and applies pressure to the piston, which moves at a rate based,at least in part, on the value of the pressure of the external fluid,the viscosity of the secondary liquid and/or the geometry of saidconduit. The conduit may include a constriction or a capillary tube.

In accordance with still further related embodiments of the invention,the one or more devices may include a second device, wherein themechanical structure of the second device separates the isolated cavityof the second device from a pressurized fluid. The isolated cavity ofthe second device is in fluidic communication with the second portion ofthe sampling chamber, such that at the end of a timing interval thetiming mechanism of the second device acts on the mechanical structureof the second device to rupture and/or collapse the mechanical structureof the second device, thus bringing the isolated cavity of the seconddevice and the second portion of the sample chamber in fluidiccommunication with the pressurized fluid. The timing mechanisms of thefirst and second device may be configured such that the mechanicalstructure of the second device ruptures and/or collapses after themechanical structure of the first device ruptures and/or collapses.

In accordance with related embodiments of the invention, the one or moredevices may include a third device having a mechanical structure influidic communication with the first portion of the sampling chamber,such that rupture and/or collapse of the mechanical structure of thethird device allows fluid communication between the first portion of thesampling chamber and a second sampling chamber. The timing mechanism ofthe third device may be configured such that the mechanical structure ofthe third device ruptures and/or collapses after the mechanicalstructure of the second device ruptures and/or collapses. The samplingchamber and/or the second sampling chamber may include a reagent.

In accordance with further related embodiments, the first portion of thesampling chamber may include a filter for retaining certain componentsfrom fluid entering the sampling chamber, the filter positioned withinthe sampling chamber such that fluid flowing between the samplingchamber and the second sampling chamber transports the retained filteredcomponents. The system may further include: a first reservoir betweenthe piston and the first portion of the sampling chamber, the firstreservoir filled with a fluid and/or a reagent solution in fluidiccommunication with the first portion, such that fluid can flow from thefirst reservoir to the first portion of the sampling chamber; and asecond reservoir in fluidic communication with the first portion ofsampling chamber, the second reservoir for receiving overflow from thefirst portion of the sampling chamber, wherein upon the collapse and/orrupture of the third devices mechanical structure, the fluid and/orreagent solution from the first reservoir flows through the filter andinto the second sampling chamber.

In accordance with yet further related embodiments of the invention, thepassive timing mechanism may include a timing diaphragm or a piston, atiming cavity and a conduit that may be a microfluidic channel or acapillary tube, and that may have a predefined geometry. Upon applyingpressure to a timing fluid within the conduit, the timing fluid advanceswithin the microfluidic channel at a speed, for example, that may bedictated by the predefined channel geometry and known timing fluidproperties. Upon the timing fluid reaching the timing cavity and fillingit after a timing interval, the timing fluid applies pressure to thetiming diaphragm or piston which ruptures and/or collapses themechanical structure thus allowing external fluid to enter the isolatedcavity. The conduit may be, without limitation, initially at leastpartially filled with the timing fluid. In other embodiments, the timingfluid may be, without limitation, the external fluid that enters fromthe isolated cavity.

In accordance with still further related embodiments of the invention,the one or more devices may include a first and second device, whereinthe isolated cavity of the first device is coupled to the timing cavityof the second device via a conduit. Upon rupture and/or collapse of themechanical structure of the first device, external fluid enters theisolated cavity of the first device and further communicates with thetiming cavity of the second device. The timing cavity of the seconddevice fills and the external fluid pressure is applied to the timingdiaphragm or piston of the second device, causing the mechanicalstructure of the second device to collapse and/or rupture.

In accordance with yet further related embodiments of the invention, thesystem further includes a controller configured to determine viscosityof the external fluid based on, at least in part, a measurementassociated with the time of rupture and/or collapse of the one or moredevices. The measurement may be an acoustic measurement, an electronicmeasurement, or an optical measurement, or a combination thereof. Thesystem may further include a third device, the isolated cavity of thesecond device in fluidic communication with the timing mechanism of thethird device, wherein the timing mechanisms of the second and thirddevices differ.

In accordance with further related embodiments of the invention, thesystem may further include a manifold. The manifold is in fluidiccommunication with the isolated cavity of each device upon ruptureand/or collapse of their associated mechanical structure. Additionally,a sampling conduit is in fluidic communication with the manifold and theexternal fluid. The sampling conduit may further be in communicationwith a reagent reservoir that holds a reagent. A mixer may be utilizedfor mixing the reagent and the fluid from the external environment. Thesampling conduit may include a sensor for performing measurements onfluid within the sampling conduit.

In accordance with still further related embodiments of the invention,the system may include a first and a second group of the one or moredevices, wherein the isolated chamber of one of the devices in the firstgroup of devices is coupled to the timing mechanism of each of thedevices in the second group, such that the mechanical structures of thesecond group rupture and/or collapse after the mechanical structure ofthe one of the devices. The external fluid of the at least one or moredevices may differ.

In accordance with further related embodiments of the invention, thesystem may further include a triggering mechanism configured to turn onand/or off the timing mechanism of at least one of the devices upon anexternal command. The triggering mechanism includes a component selectedfrom a check valve, a solenoid valve, a one-shot valve, a fluidicswitch, a MEMS component, a detonator and any combination thereof.

In accordance with another embodiment of the invention, a method fordetermining viscosity of an external fluid is provided. The methodincludes deploying a system in an external fluid, the system including aplurality of devices. An isolated cavity of a first device is opened ata time determined by an electrically passive timing mechanism of thefirst device, such that the external fluid enters the isolated cavity ofthe first device. The isolated cavity of the first device is in fluidiccommunication with a timing mechanism of the second device. An isolatedcavity of a second device is opened at a time determined by the timingmechanism of the second device. Viscosity of the external fluid isdetermined based on, at least in part, a measurement associated with theopening of the isolated cavities of the first and second devices.

In accordance with related embodiments of the invention, the passivetiming mechanism of each device may include a timing diaphragm or apiston, a timing cavity; and a conduit in fluidic communication with thetiming cavity. Upon applying pressure to a timing fluid within theconduit, said timing fluid advances within the conduit and upon reachingthe timing cavity and filling it after a timing interval, the timingfluid applies pressure to the timing diaphragm or piston which rupturesand/or collapses the mechanical structure thus allowing external fluidto enter the isolated cavity.

In accordance with further related embodiments of the invention,determining viscosity may include performing a measurement, such as anacoustic measurement, an electronic measurement, an optical measurement,or combinations thereof.

In still further related embodiments of the invention, the isolatedcavity of the second device is in fluidic communication with a timingmechanism of a third device. The method further includes opening anisolated cavity of the third device, at a time determined by the timingmechanism of the third device, wherein the timing mechanisms of thesecond and third devices differ. Determining viscosity of the externalfluid may be based on, at least in part, a measurement associated withthe opening of the isolated cavities of the first, second and thirddevices.

In accordance with another embodiment of the invention, a methodincludes deploying a system in an external fluid, the system includingone or more devices. An isolated cavity of a first device of the one ormore devices is opened, at a time determined by an electrically passivetiming mechanism of the first device, such that the external fluidenters the isolated cavity of the first device, the isolated cavity ofthe first device in fluidic communication with a sampling chamber.

In accordance with related embodiments of the invention, the samplingchamber may include one or more chemical and/or biological reagents. Themethod may include filtering the fluid upon or prior to entering thesampling chamber. The filter may be a mechanical filter, a solid phaseextraction column, a hydrocarbon filter, a gas chromatographypreconcentrator, a packed column, a filter that collects andconcentrates radioactive material, a biological filter, an absorbentmedium, a scavenging medium, a hydrophobic material, a hydrophilicmaterial, or combination thereof. The method may include preventingbackflow of the fluid from the sampling chamber to the isolated cavity.

In accordance with yet further related embodiment of the invention, thesampling chamber of the first device may include a piston and/or aflexible membrane that separates the sampling chamber into a firstportion and a second portion, the first portion in fluidic communicationwith the isolated cavity. The second portion may be in fluidiccommunication with an auxiliary chamber via a conduit, wherein thesecond portion is initially filled with a secondary liquid, and whereinupon opening the isolated cavity of the first device, the external fluidenters the first portion of the sampling chamber and applies pressure tothe piston, which moves at a rate based, at least in part, on the valueof the pressure of the external fluid, the viscosity of the secondaryliquid and/or the geometry of said conduit.

In accordance with still further related embodiments of the invention,the one or more devices may include a second device, an isolated cavityof the second device in fluidic communication with the second portion ofthe sampling chamber. The method may further include opening theisolated cavity of a second device, at a time determined by a timingmechanism of the second device, bringing the isolated cavity of thesecond device and the second portion of the sample chamber in fluidiccommunication with a pressurized fluid. The timing mechanisms of thefirst and second device are configured such that the mechanicalstructure of the second device ruptures and/or collapses after themechanical structure of the first device ruptures and/or collapses.

In accordance with further embodiments of the invention, the one or moredevices may include a third device having a mechanical structure influidic communication with the first portion of the sampling chamber.The method further includes rupturing and/or collapsing the mechanicalstructure of the third device, allowing fluid communication between thefirst portion of the sampling chamber and a second sampling chamber. Atiming mechanism of the third device is configured such that themechanical structure of the third device ruptures and/or collapses afterthe isolated cavity of the second device opens. The sampling chamberand/or the second sampling chamber may include a reagent.

In accordance with still further related embodiments of the invention,the method may include filtering components from fluid entering thesampling chamber, the filtering positioned within the sampling chambersuch that fluid flowing between the sampling chamber and the secondsampling chamber includes the filtered components. There may be a firstreservoir between the piston and the first portion of the samplingchamber, the first reservoir filled with a fluid and/or a reagentsolution in fluidic communication with the first portion, such thatfluid can flow from the first reservoir to the first portion of thesampling chamber. There may be a second reservoir in fluidiccommunication with the first portion of sampling chamber, the secondreservoir for receiving overflow from the first portion of the samplingchamber, wherein upon opening the third devices mechanical structure,the fluid and/or reagent solution from the first reservoir flows throughthe filter and into the second sampling chamber.

In accordance with another embodiment of the invention, an electricallypassive sampling device such as in the described-above embodiments, maybe used to sample fluid in highly flammable or explosive environment,such as refinery equipment, pipes and tanks, fuel tanks, gas tanks,oilfield separation reservoirs, oilfield production and explorationrigs, oilfield wellhead equipment. The intrinsic electrically-passivenature of the device assures that no electrical spark risk is present,by design. Such a sampling device may furthermore be used to acquireindividual samples at different times, or at different depths. Thiswould allow, for example, the acquisition of samples at different depthswithin a refinery tank to understand the details of the compositionvariations by depth, or of the stratification that may take place insuch tanks.

In accordance with another embodiment of the invention, an electricallypassive sampling device such as in the described-above embodiments, maybe placed near a nuclear facility, in an atmospheric and/or aquaticenvironment, the start of the sampling program being triggered upon theoccurrence of an external event such as, without limitation, an accidentalert, a power outage, a military attack, a terrorist attack and/or anatural disaster.

In accordance with another embodiment of the invention, an electricallypassive device/system such as in the described-above embodiments, isdeployed in an urban or suburban location, the start of the samplingprogram being triggered upon the occurrence of an external event suchas, without limitation, an accident alert, a chemical accident, anuclear accident, a military attack, a terrorist attack and/or a naturaldisaster.

In accordance with another embodiment of the invention, an electricallypassive device/system such as in the described-above embodiments, ismounted on a water supply line or pipe. Sampling may be triggered by anexternal event such as, without limitation, a user signal, a signal froman in-line measurement system, an external event such as an accidentalert, a military attack, a terrorist attack and/or a natural disaster.

In accordance with another embodiment of the invention, an electricallypassive device/system such as in the described-above embodiments, ismounted on a ground-based or aerial vehicle, robot or drone. Samplingmay be triggered by an external event such as, without limitation, auser signal, a signal from an in-line measurement system, an externalevent such as an accident alert, a military attack, a terrorist attackand/or a natural disaster.

In accordance with another embodiment of the invention, an electricallypassive device/system such as in the described-above embodiments, ismounted on a submerged device such as, without limitation, a mechanicalstructure, a rig, a cable, a submarine, a remotely operated underwatervehicle, an autonomous underwater vehicle, a glider, a ship or a buoy.Sampling may be triggered by an external event such as, withoutlimitation, a user signal, a signal from an in-line measurement system,a signal from the submerged device, a fluorescence signal, an externalevent such as an accident alert, a military attack, a terrorist attackand/or a natural disaster.

In accordance with another embodiment of the invention, a multitude ofdevices/systems such as in the above-described embodiments may bedeployed at different locations surrounding a structure to be monitored,such that the data collected from analyzing the different samples,either in-situ or after retrieval, is used to generate a map of theevolution of the component of interest in multiple dimensions (up tothree spatial coordinates and time). Example could be the monitoring ofthe pollution generated by an offshore oil well, from a tanker or pipeaccident, from a chemical plant, from a nuclear power plant, from cartraffic, contamination from a military attack or from a terrorist attackand/or a natural disaster.

In accordance with another embodiment of the invention, a method foracquiring at least one sample from a fluid is provided. The methodincludes deploying at least one device in the fluid. Each deviceincludes a sampling mechanism having an isolated cavity that isinitially inaccessible to the external fluid; an electrically passivetiming mechanism including a piercing structure; and a mechanicalstructure separating the isolated cavity from the exterior environment.At the end of a timing interval the piercing structure of the timingmechanism pierces the mechanical structure, bringing the isolated cavityin contact with the external fluid.

In accordance with related embodiments of the invention, the timinginterval may be less than 100 ms. The method may further include storinga sample of the fluid within the cavity. The passive timing mechanismmay include a piston. The method may further include emitting by thedevice an acoustic signature when the mechanical structure is pierced.

In accordance with further related embodiments of the invention, thepiston may be configured to move within the isolated cavity, the timingmechanism may be configured to advance the piston, and advancement ofthe piston causes the piercing structure to pierce the mechanicalstructure. The piston may include the piercing structure. The timingmechanism may include a conduit, the method further including applyingpressure to a timing fluid within the conduit causing the piston toadvance such that the piercing structure pierces the mechanicalstructure, allowing external fluid to enter the isolated cavity. Thetiming mechanism may include a timing cavity, the conduit in fluidiccommunication with the timing cavity, the method further comprisingapplying pressure to the timing fluid within the conduit such that thetiming fluid advances within the conduit and upon reaching the timingcavity and filling it after a timing interval, the timing fluid appliespressure to a side of the piston, causing the piston to advance suchthat the piercing structure pierces the mechanical structure, allowingexternal fluid to enter the isolated cavity. The timing interval may bepredetermined based, at least in part, on geometry of the channel,volume of the timing cavity, pressure applied to the timing fluid, ortiming fluid properties, or any combination thereof. The at least onedevice may include a plurality of sampling mechanisms having varyingtiming cavity volumes.

In accordance with yet further related embodiments of the invention, atleast one of the one or more devices includes a plurality of samplingmechanisms having varying timing intervals. The timing mechanism of eachsampling mechanism may include a timing cavity, and a conduit in fluidiccommunication with the timing cavity, the method further comprisingapplying pressure to a timing fluid within the conduit, such that thetiming fluid advances within the conduit and fills the timing cavity,the timing interval of each sampling mechanism may be predeterminedbased, at least in part, the volume of the timing cavity, and whereinthe plurality of sampling mechanisms have varying timing cavity volumes.

In accordance with still further related embodiments of the invention,the sampling mechanism further includes a sampling chamber coupled tothe isolated cavity. The method may further include decoupling thesampling chamber from the isolated cavity.

Accordance with further related embodiments of the invention, the methodmay include applying a trigger signal to start the timing mechanism. Theone or more devices may include a first device and a second device, andwherein applying the trigger signal to the second device is based, atleast in part, on the acquisition of a sample by the first device. Atleast one of the one or more devices may include a first samplingmechanism and a second sampling mechanism, and wherein applying thetrigger signal to the second sampling mechanism is based at least inpart, on the acquisition of a sample by the first sampling mechanism.

In accordance with yet further related embodiments of the invention, themethod may further include recording sample acquisition time of eachsample. Each sampling mechanism may include a sample chamber for storingan acquired sample, the method further including monitoring the samplechamber using one of an optical sensor, a conductivity sensor, atemperature sensor, a force sensor, a deflection sensor, a chemicalsensor, a biological sensor, a pressure sensor and a pressure switch, ora combination thereof, so as to detect the acquired sample. Each devicemay include a sample chamber for storing an acquired sample, the samplechamber at least partially filled with a culture medium, a chemicalreagent or a biological reagent, or a combination thereof.

In accordance with an embodiment of the invention, a system foracquiring samples in a body of fluid includes a containment unit that isnegatively buoyant relative to the body of fluid. A sampling array istethered to the containment unit, the sampling array including aplurality of sampling devices positioned along the array, for samplingthe body of fluid at varying depths.

In accordance with related embodiments of the invention, the samplingarray may include a buoyancy device. One or more of the sampling devicesmay be positively buoyant relative to the body of fluid. The system mayinclude a latching mechanism for releasably holding the tetheredsampling array in an initial position relative to the containment unit.A trigger mechanism may control the latching mechanism to release thesampling array, wherein the sampling array, still tethered to thecontainment unit at a first end, ascends in the body of fluid. Thetrigger mechanism may control the latching mechanism by providing to thelatching mechanism an acoustic signal, an electric signal, an opticalsignal, an electromagnetic signal, or a mechanical signal, or acombination thereof. The containment unit may include a receiver forreceiving a control signal that may be an acoustic signal or an opticalsignal, the trigger mechanism controlling the latching mechanism as afunction of the control signal. The trigger mechanism may check atpredefined times for receipt of the control signal, and if the controlsignal is not received after a period of time, the trigger mechanismcontrols the latching mechanism so as to release the sampling array,such that the sampling array, still tethered to the containment unit atthe first end, ascends in the body of fluid. The system may furtherinclude a surface buoyancy device configured to remain at the surface ofthe body of fluid, the surface buoyancy device including atransmitter/receiver device configured to receive a deployment signal,and upon receipt of the deployment signal, transmit a control signal tothe trigger mechanism, causing the trigger mechanism to release thesampling array, such that the sampling array, still tethered to thecontainment unit at the first end, ascends in the body of fluid. Thetrigger mechanism may include an acoustic release, a device commonlyused in fields such as oceanography. The latching mechanism may includea fusible wire and means of sending an electrical current through thefusible wire, leading to the melting of the fusible wire and the releaseof the sampling array. The latching mechanism may further include meansto providing mechanical advantage to the strength of the fusible wire.

In accordance with further related embodiments of the invention, uponeach sampling device acquiring all their samples, the sampling array maybe configured to automatically release from its tether with thecontainment unit. The sampling array may include a Global PositioningSystem (GPS), and a transmitter for transmitting GPS coordinates. Thesystem may further include an installation/retrieval tether and thecontainment unit may include a latch mechanism for releasably connectingthe tether.

In accordance with still further related embodiments of the invention,the sampling array may include an accelerometer, a tiltmeter, agyroscope, a relative bearing device, an inclinometer, or a compass, orany combination thereof, for providing positional information of thesampling array relative to the containment unit. The system may furtherinclude a memory device for recording the positioning information.

In accordance with yet further related embodiments of the invention,each sampling device may include one or more sampling mechanisms eachhaving an electronically passive timing mechanism, each samplingmechanism configured to acquire a sample at a time determined by theirassociated electronically passive timing mechanism. Each samplingmechanism may further include an isolated cavity that is initiallyinaccessible to an external fluid, and a mechanical structure separatingthe isolated cavity from the exterior environment, wherein at the end ofa timing interval the timing mechanism pierces the mechanical structure,bringing the isolated cavity in contact with the body of fluid. Eachsampling mechanism may further include a trigger mechanism fortriggering each timing mechanism. Each timing mechanism may beconfigured to be triggered upon deployment of the system in the body offluid.

In accordance with further related embodiments of the invention, thesystem may further include a monitoring system for recording sampleacquisition time of each acquired sample. Each sampling device mayinclude a sample chamber for storing an acquired sample, and themonitoring system includes one of an optical sensor, a conductivitysensor, a temperature sensor, a force sensor, a deflection sensor, achemical sensor, a biological sensor, a pressure sensor and a pressureswitch, or a combination thereof. Each sampling device may include asample chamber for storing an acquired sample, the sample chamber atleast partially filled with a chemical reagent, an absorption medium, abiocide, a biological reagent, or a combination thereof. The system mayfurther include a secondary buoyancy device held in an undeployedposition within or proximate the containment unit, the secondarybuoyancy device configured upon activation to extend to the surface ofthe body of fluid via a tether attached to the containment unit, suchthat the tether can be retrieved on the surface along with thecontainment unit.

In accordance with another embodiment of the invention, a method foracquiring samples in a body of fluid is provided. The method includesdeploying a containment unit that is negatively buoyant relative to thebody of fluid, a sampling array tethered to the containment unit, thesampling array including a plurality of sampling devices positionedalong the array, for sampling the body of fluid at varying depths.

In accordance with related embodiments of the invention, the samplingarray may include a buoyancy device. One or more of the sampling devicesmay be positively buoyant relative to the body of fluid.

In accordance with further related embodiments of the invention, thesampling array may be buoyant relative to the body of fluid, and thecontainment unit includes a latching mechanism for releasably holdingthe tethered sampling array in an initial position relative to thecontainment unit, the method further including controlling the latchingmechanism so as to release the sampling array, such that the samplingarray, still tethered to the containment unit at a first end, ascends inthe body of fluid. Controlling the latching mechanism may includeproviding to the latching mechanism an acoustic signal, an electricsignal, an optical signal, an electromagnetic signal, or a mechanicalsignal, or a combination thereof. The containment unit may include areceiver for receiving a control signal selected from the groupconsisting of an acoustic signal and an optical signal, and whereincontrolling the latching mechanism is based, at least in part, onreceipt of the control signal by the receiver. The method may furtherinclude: checking, by the receiver at predefined times, for receipt ofthe control signal; and, if the control signal is not received by thereceiver after a predetermined period of time, controlling the latchingmechanism to release the sampling array, such that the sampling array,still tethered to the containment unit at the first end, ascends in thebody of fluid. The trigger mechanism may include an acoustic release, adevice commonly used in fields such as oceanography. The latchingmechanism may include a fusible wire and means of sending an electricalcurrent through the fusible wire, leading to the melting of the fusiblewire and the release of the sampling array. The latching mechanism mayfurther include means to providing mechanical advantage to the strengthof the fusible wire.

In accordance with further related embodiments of the invention, themethod may further include deploying a surface buoyancy deviceconfigured to remain at the surface of the body of fluid, the surfacebuoyancy device including a transmitter/receiver device, the containmentunit including a receiver device. The method further includes: receivingat the transmitter/receiver device a trigger signal; transmitting, bythe transmitter/receiver device, a command signal to the containmentunit upon receipt of the trigger signal; and receiving, by the receiverdevice, the command signal, whereupon the latching mechanism iscontrolled to release the sampling array, such that the sampling array,still tethered to the containment unit at the first end, ascends in thebody of fluid.

In accordance with still further related embodiments of the invention,the method may further include, upon each sampling device acquiring alltheir samples, releasing the sampling array from its tether with thecontainment unit, such that the sampling array ascends to the surface.The sampling array may include a Global Positioning System (GPS) and atransmitter, the method further including transmitting the GPScoordinates via the transmitter.

In accordance with yet further related embodiments of the invention, themethod may include determining position information of the samplingarray relative to the containment unit. Determining position informationof the sampling array relative to the containment unit may include usingan accelerometer, a tiltmeter, a gyroscope, a relative bearing device,an inclinometer, or a compass, or any combination thereof, so as toprovide positional information of each sampling device of the samplingarray relative to the containment unit. The position information may bestored on a memory device.

In accordance with further related embodiments of the invention, eachsampling device may include one or more sampling mechanisms each havingan electronically passive timing mechanism. The method may furtherinclude acquiring, by each sampling mechanism, a sample at a timedetermined, at least in part, by their associated electronically passivetiming mechanism. Each sampling mechanism may further include: anisolated cavity that is initially inaccessible to an external fluid; anda mechanical structure separating the isolated cavity from the exteriorenvironment, the method further including, at the end of a timinginterval determined by the timing mechanism, piercing the mechanicalstructure, bringing the isolated cavity in contact with the body offluid. The method may include triggering each timing mechanism so as tostart the timing interval. Each timing mechanism may be configured to betriggered upon deployment of the system in the body of fluid.

In accordance with still further related embodiments of the invention,the method may further include determining sample acquisition time ofeach acquired sample, and storing the determined sample acquisitiontimes in a memory device. Each sampling device may include a samplechamber for storing an acquired sample, wherein determining sampleacquisition time of each sample includes using one of an optical sensor,a conductivity sensor, a temperature sensor, a force sensor, adeflection sensor, a chemical sensor, a biological sensor, a pressuresensor and a pressure switch, or a combination thereof. Each samplingdevice may include a sample chamber for storing an acquired sample, thesample chamber at least partially filled with a chemical reagent, anabsorption medium, a biocide, a biological reagent, or a combinationthereof.

In accordance with yet further related embodiments of the invention, themethod may further include holding a secondary buoyancy device in anundeployed position within or proximate the containment unit; releasingthe secondary buoyancy device via a tether attached to the containmentunit so that it reaches the surface of the body of fluid; and retrievingthe tether along with the containment unit.

In accordance with further related embodiments of the invention,deploying the containment unit may include positioning the containmentunit so that it rests at a predetermined position on the bottom floor ofthe body of fluid. Positioning the containment unit may include usingone of a surface vessel or a remotely operated underwater vehicle (ROV),or a combination thereof. Positioning the containment unit may includeusing a GPS system.

In accordance with another embodiment of the invention, a deviceincludes an isolated cavity that is initially inaccessible to theexternal fluid. The device includes a device body including one or morestructural elements supporting a mechanical structure, the mechanicalstructure separating the isolated cavity from the external fluid. Thedevice further includes a piercing structure for piercing the mechanicalstructure, and an electrically passive timing mechanism including afluidic timing cavity. At the end of a timing interval fluid within thetiming cavity causes a piercing structure to pierce the mechanicalstructure, causing the mechanical structure to collapse, rupture and/orfracture, wherein an acoustic signal is emitted when the mechanicalstructure is pierced.

In accordance with related embodiments of the invention, the structuralelements may be made of a material that is different from the mechanicalstructure. The structural elements may include a ceramic, a metal, aplastic or a resin, or combinations thereof, and the mechanicalstructure may include silicon, a ceramic, a sapphire or glass, orcombinations thereof.

In accordance with further related embodiments of the invention, thestructural elements, the mechanical structure, the timing mechanismand/or the piercing structure may be manufactured using additivemanufacturing technologies. The additive manufacturing technology may bestereolithography, polyjet, inkjet printing, plastic laser sintering,direct metal laser sintering, fused deposition modeling, 3D printing inceramic technology, or combinations thereof. The structural elements,mechanical structure, timing mechanism, and/or piercing structure may bemanufactured using MEMS etching techniques such as deep reactive ionetching, inductively coupled plasma reactive ion etching, isotropic wetetching, anisotropic wet etching or combinations thereof.

In accordance with still further related embodiments of the invention,the mechanical structure may be more brittle than the structuralelements. The piercing structure may be made from a material that isdifferent from the mechanical structure. The piercing structure may bemade from the same material as the structural elements. The piercingstructure and the structural elements may be coupled via linkages thatpermit movement of the piercing structure. The piercing structure, thestructural elements and the linkages may be manufactured monolithically.

In accordance with yet further related embodiments of the invention, themechanical structure has a top and bottom surface, the top surface forfacing the external fluid and the bottom surface for facing the piercingstructure, wherein the mechanical structure may include partially etchedgeometry on the top surface and/or the bottom surface.

In accordance with further related embodiments of the invention, theexternal fluid entering the fluidic timing cavity may apply pressure toa timing diaphragm and/or piston so as to drive the piercing structureinto the mechanical structure, causing the mechanical structure tocollapse, rupture or fracture. The timing diaphragm may include a metal,a polymer, or a combination thereof. The electrically passive timingmechanism may include a porous structure and/or material that allows theexternal fluid to seep into the fluidic timing cavity, at a slow rate,causing the mechanical structure to collapse, rupture or fracture aftera time delay. The electrically passive timing mechanism may include afluidic circuit that allows the external fluid to enter the fluidictiming cavity at a slow rate, causing the mechanical structure tocollapse, rupture or fracture after a time delay.

In accordance with still further related embodiments of the invention, amethod of making the device may include using MEMS etching techniques.The MEMS etching techniques may include deep reactive ion etching,inductively coupled plasma reactive ion etching, isotropic wet etching,anisotropic wet etching, or combinations thereof, which may be used tomake the structural elements, the piercing structure, the passive timingmechanism and/or the mechanical structure.

In accordance with yet further related embodiments, a method of makingthe device includes using an additive manufacturing technology. Theadditive manufacturing technology may include stereolithography,polyjet, inkjet printing, laser sintering, fused deposition modeling, 3Dprinting, or combinations thereof, which may be used to make thestructural elements, the piercing structure, the passive timingmechanism, and/or the mechanical structure. The structural elements mayinclude a metal, a ceramic, a plastic a resin, or combinations thereof,with the mechanical structure including silicon, ceramic, sapphire, orcombinations thereof. The method may further include using MEMStechnology to make the mechanical structure.

In accordance with still further related embodiments of the invention,the mechanical structure has a top and bottom surface, the top surfacefor facing the external fluid and the bottom surface for facing thepiercing structure, wherein a method of making the device includespartially etching the top surface and/or the bottom surface.

In accordance with yet further related embodiments of the invention, amethod of making the device includes coupling the piercing structure andthe structural elements via linkages so as to permit movement of thepiercing structure. The method may further include monolithicallymanufacturing the piercing structure and the structural elements.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing features of the invention will be more readily understoodby reference to the following detailed description, taken with referenceto the accompanying drawings.

FIG. 1 shows deployment of a device for use in sampling hydrocarbonsduring fracturing or fluid injection operations, in accordance with anembodiment of the invention.

FIGS. 2(a-d) show the device of FIG. 1 in more detail, in accordancewith an embodiment of the invention. FIG. 2(a) shows the device prior toactivation. FIG. 2(b) shows the device with the isolation membranecollapsed. FIG. 2(c) shows the device with the sample chamber filledwith sample fluid. FIG. 2(d) shows the device ready to be interrogatedafter surface retrieval.

FIG. 3(a) shows a burst of acoustic energy resulting from the rupturingof an isolation membrane, in accordance with an embodiment of theinvention. FIG. 3(b) shows multiple microphones placed at differentpositions in the formation, for recording the arrival time of thewavefronts caused by ruptured isolation membranes, in accordance with anembodiment of the invention.

FIG. 4 shows a passive timing device that includes a pharmaceuticalproduct for release within a human body, in accordance with anembodiment of the invention.

FIG. 5 shows a passive timing device that includes a filter forcontaining the broken diaphragm particles, in accordance with anembodiment of the invention.

FIG. 6 shows integration of a plurality of sampling devices and/ormechanisms within an oilfield-sampling tool, in accordance with anembodiment of the invention.

FIG. 7 shows an array of smart sampling devices embedded within anunderwater measurement system which may be attached with a cable toeither a buoy, a rig, a vessel or a ship, in accordance with anembodiment of the invention.

FIG. 8A shows a viscosity measurement system that may be fully passive,in accordance with an embodiment of the invention. FIG. 8B shows anotherviscosity-measurement system, in accordance with an embodiment of theinvention.

FIG. 9A shows a sampling and measurement system that includes amanifold, in accordance with an embodiment of the invention. FIG. 9Bshows an external sampling conduit connected via a T-junction to areagent reservoir, in accordance with an embodiment of the invention.

FIG. 10A shows a device that may be used to acquire a sample from acontaminated external fluid, in accordance with an embodiment of theinvention. FIG. 10B shows the device of FIG. 10A after sampling, inaccordance with an embodiment of the invention.

FIGS. 11A-C shows a system capable of acquiring a sample from anexternal fluid, and maintaining it at a desired pressure for extendedperiods of time, in accordance with an embodiment of the invention. FIG.11A shows the system prior to acquiring a sample. FIG. 11B shows thesystem after acquiring the sample. FIG. 11C shows the system aftersample pressurization.

FIG. 12A shows a device for performing a sampling operation from ahigh-pressure external fluid without shocking the fluid, in accordancewith an embodiment of the invention. FIG. 12B shows the device of FIG.12A that further allows the sample to be maintained at a high pressureafter sampling, in accordance with an embodiment of the invention.

FIGS. 13A-D show, in chronological order, operations performed by asystem that, in addition to sampling at a time controlled by a passivetiming mechanism, integrates a mechanism allowing the subsequenttransfer of the sample from an initial sampling chamber to anothersampling chamber after a given amount of time, in accordance with anembodiment of the invention. FIG. 13A shows the system prior toacquiring a sample. FIG. 13B shows the system after collapse of a firstdevice's mechanical structure. FIG. 13C shows the system after the latercollapse of a second device's mechanical structure. FIG. 13D shows thesystem after the later collapse of a third device's mechanicalstructure. FIG. 13E shows the system of FIGS. 13A-D modified such thatthe sampling chamber 1305 including a first reservoir and a secondreservoir.

FIG. 14 shows multiple sampling systems connected in a “Daisy-chain”configuration, in accordance with an embodiment of the invention.

FIG. 15 shows a system capable of controlling the sampling times of aplurality of sampling devices using a trigger device, in accordance withan embodiment of the invention.

FIG. 16(a) shows a sampling device that uses a piston in place of atiming diaphragm, and includes an optional triggering system, inaccordance with an embodiment of the invention. FIG. 16(b) shows thesampling device from FIG. 16A after the piston has pierced themechanical structure, thus enabling the acquisition of a sample, inaccordance with an embodiment of the invention.

FIG. 17 shows a sampling device that includes an optional triggeringsystem, which performs a sample acquisition within a given timeinterval, in accordance with an embodiment of the invention.

FIG. 18 shows a sampling device similar to that embodiment shown in FIG.17, but with the timing mechanism modified in such a way that the sampleacquisition is performed in a much shorter time interval, in accordancewith an embodiment of the invention.

FIG. 19 shows a sampling device consisting of two sampling mechanismswhereas the timing of the two sampling mechanisms is different due totheir different timing cavity volume, in accordance with an embodimentof the invention.

FIG. 20 shows the installation of a sampling system by a deploymentvessel, in accordance with an embodiment of the invention. Theinstallation requires accurate positioning of the system on the seafloor and may optionally be aided by an ROV for disconnection from thesurface tether and/or accurate placement relative to the wellhead.

FIG. 21 shows an array of sampling systems that are installed in standbymode around an oil rig or offshore platform, in accordance with anembodiment of the invention. At the surface facility, an acoustictransmitter/receiver continuously or at pre-defined time intervalstransmits an acoustic signal. This signal can be detected by thesampling systems, which indicates normal operation on surface, thus thesystems will not deploy and will remain in standby mode.

FIG. 22 shows the embodiment of FIG. 21 where there is a loss oftransmitted signal from the surface facility, in accordance with anembodiment of the invention. This may be indicative of an abnormalsituation at surface. The systems may continue to attempt detection ofthe acoustic source from surface for a period of time. If there is acontinued period of loss of transmitted signal, the sampling systemswill be triggered to deploy and commence monitoring.

FIG. 23 shows sampling arrays after deployment due to loss oftransmitted signal from the surface facility, in accordance with anembodiment of the invention. Upon deployment of the sampling arrays,each sample device may automatically start sample acquisition atpredefined timing intervals.

FIG. 24 shows how a specific configuration of the sampling arrays may bevaried according to the location relative to the wellhead, in accordancewith an embodiment of the invention. This may serve to effectivelyincrease sampling resolution.

FIG. 25 shows the effect that ocean currents or other movement in thewater column may have on the positioning of the sampling arrays, and howcompensation using accelerometers, relative bearing meters or similardevices may be used to accurately determine the position of each pointin the sampling array over time, in accordance with an embodiment of theinvention.

FIG. 26 shows the sampling systems after sampling has been completed andseveral options for retrieval of the sampling string and/or samplingsystem on the surface, in accordance with an embodiment of theinvention.

FIG. 27(a) shows an override signal being emitted by a transmitter atthe surface and detected by the sampling systems, in accordance with anembodiment of the invention. FIG. 27(b) shows the override signalactivating a buoyancy device to carry a retrieval tether to the surfacefor subsequent retrieval of the unactivated sampling systems from a bodyof water, in accordance with an embodiment of the invention.

FIG. 28 shows a sampling system in standby mode having an additionalbuoyancy device which remains at ocean surface level, and includes adata transmitter/receiver device, so that when a trigger signal isreceived, the device is able to send a deployment command via a cable totrigger the sampling system and/or release the sampling deploymentbuoyancy device, in accordance with an embodiment of the invention.

FIG. 29 shows additional sampling systems (or rapid deployment kits)which may be deployed at a greater perimeter from the wellhead after apollution event has occurred for additional leak monitoring, inaccordance with an embodiment of the invention.

FIG. 30 shows details of a sampling system, in accordance with anembodiment of the invention.

FIG. 31 shows a timestamping and sample acquisition monitoring systemthat allows the determination of the timestamp of each sampleacquisition and of different other parameters related to the sampleacquisition process based on measurements of pressure levels within thesample chamber and, optionally, in the external fluid, in accordancewith an embodiment of the invention.

FIG. 32 shows a sampling device implementing a passive timing mechanismallowing the timing of a sample acquisition to be triggered by theacquisition of the previous sample, in accordance with an embodiment ofthe invention.

FIG. 33 shows sampling devices described in the embodiment of FIG. 32connected together so as to trigger each other, in accordance with anembodiment of the invention.

FIG. 34 shows sampling devices described in the embodiment of FIG. 32connected together so as to trigger each other, further shows amanifold, in accordance with an embodiment of the invention.

FIG. 35 shows a device wherein the structural elements of the devicebody and the mechanical structure are monolithic, in accordance with anembodiment of the invention.

FIG. 36 shows a device wherein the structural elements of the devicebody and the mechanical structure are manufactured separately, inaccordance with an embodiment of the invention.

FIG. 37 shows the structural elements of the device body of FIG. 36incorporating additional protection features, in accordance with anembodiment of the invention.

FIG. 38 shows a device wherein the structural elements of the devicebody and the timing diaphragm 3802 are monolithic, in accordance with anembodiment of the invention.

FIG. 39 shows a device wherein the structural elements of the devicebody of FIG. 38 incorporate additional protection features for themechanical structure and for the timing mechanism, in accordance withvarious embodiments of the invention.

FIG. 40 shows a device in which the structural elements, timingdiaphragm, and piercing structure are manufactured monolithically, inaccordance with an embodiment of the invention.

FIG. 41 shows structural elements of the device body of FIG. 40incorporating additional protection features for the mechanicalstructure and timing mechanism.

FIG. 42A shows a lateral cross-section of a device where the structuraldevice body parts and the piercing structure are manufacturedmonolithically, in accordance with an embodiment of the invention. FIGS.42B and 42C show top views of the device presented in FIG. 42A,exemplifying possible hinge geometries, in accordance with variousembodiments of the invention.

FIG. 43 shows a device where the structural elements/body parts andtiming diaphragm are built monolithically, but integrating also thetiming cavity 4302, in accordance with an embodiment of the invention.

FIG. 44 shows a device similar to FIG. 43, where the monolithic part ofthe device further incorporates the piercing structure, in accordancewith an embodiment of the invention.

FIG. 45 shows a device where the mechanical structure further includesan etched geometry on the top surface, near the center, in accordancewith an embodiment of the invention.

FIG. 46 shows a device where the mechanical structure further includesan etched geometry on the bottom surface, near the outer edge, inaccordance with an embodiment of the invention.

FIG. 47A shows typical elastic deflection of a circular clamped membraneunder hydrostatic pressure applied to the top side, in accordance withan embodiment of the invention. FIG. 47B shows a cross-section through acircular mechanical structure, and one possible positioning of thetop-side etched geometry, in accordance with an embodiment of theinvention. FIGS. 47C, 47D, 47E shows top views of possible top-sideetched geometries, in accordance with various embodiments of theinvention.

FIG. 48A shows a mechanical structure geometry which has a membrane-likeportion delimited by etching, in accordance with an embodiment of theinvention. FIGS. 48B and 48C show additional exemplary geometries of themembrane-like portion of the mechanical structure, in accordance withvarious embodiments of the invention.

FIG. 49 show different ways to manufacture the passive timing mechanismof the device, in accordance with various embodiments of the invention.More particularly, FIG. 49A shows the passive timing mechanism as aporous structure. FIG. 49B shows the timing cavity integrated to thepassive timing mechanism. FIG. 49C show the passive timing mechanism asa fluidic circuit wherein the timing cavity is not integrated to thepassive timing mechanism. FIG. 49D shows the passive timing mechanism asa fluidic circuit wherein the timing cavity is integrated to the passivetiming mechanism.

FIG. 50 shows the device of FIG. 35, but where the timing diaphragm isreplaced by a piston structure, in accordance with an embodiment of theinvention.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

In illustrative embodiments, an electrically passive device and methodfor in-situ acoustic emission, and/or releasing, sampling and/ormeasuring of a fluid or various material(s) is provided. The device mayprovide a robust timing mechanism to release, sample and/or performmeasurements on a predefined schedule, and, in various embodiments,emits an acoustic signal sequence(s) that may be used for triangulationof the device position within, for example, a hydrocarbon reservoir or aliving body. Details are discussed below.

FIG. 1 shows deployment of a device 105 for use in sampling hydrocarbonsduring fracturing or fluid injection operations, in accordance with anembodiment of the invention. It should be noted that discussion of thespecific device 105 shown, for use in sampling hydrocarbons, is forillustrative purposes only. Other device configurations and applicationsare within the scope of the present invention. For example, the device105 may be deployed in a wide range of environments including, withoutlimitation, within a pipe, a well, an engine, a hydrocarbon reservoir,an aquifer, a body of water, an oil field tool, a waste disposalreservoir, a proppant formulation and a living body to release, sampleor measure various fluids (including a gas) or other material(s).

The device 105 may be deployed, without limitation, in downhole fluid101 within a fracture in an underground formation. The device may be,for example, pumped or otherwise injected, into the rock matrix. Thedevice 105 may work in combination with conventional oilfieldmeasurement tools 103 or autonomous battery-operated sensors, that maybe placed in the well in hydraulic communication with the fracture wherethe device 105 is injected. The device 105 may be used at very highpressures or temperatures, thus providing a pathway to performingmeasurements within wells which are currently inaccessible to existingsensor technology due to, without limitation, severely constrainedgeometry, corrosive fluids, elevated pressure and/or temperature.Examples of adverse well environments include recently developeddeep-sea well reservoirs in the Gulf of Mexico. The device 105 may beused in areas with no available power. The device 105 may be used inexplosive environments or atmospheres, where electric equipment poses arisk of explosion. The device 105 may be used for water and/or airquality monitoring in and around cities, chemical plants, nuclear sites,offshore platforms and other oilfield structures, military missions andbattlegrounds. The device 105 may be used in robots such as marineremotely-operated underwater vehicles, autonomous underwater vehicles,airborne or ground drones and vehicles, and other types of roboticequipment. The device 105 may be used where and/or when there is nopower available, such as in certain remote area.

The device may be of any size, dependent for example, on theapplication. In various embodiments, the device may be fabricated, atleast in part, using micromachining or micro system technology, using,for example, silicon, glass and/or ceramics. In various embodiments,certain portions of the device may not be included in the micromachinedprocess, such as the sampling chamber (described in more detail below),which may be, for example, a separate vial or other container.

FIGS. 2(a-d) show the device in more detail, in accordance with variousembodiments of the invention. FIG. 2(a) shows the device 200 prior toactivation. The device 200 includes at least one sampling mechanism forobtaining a sample of the external oil-well fluid 210.

In illustrative embodiments, the sampling mechanism includes amicrofluidic timing mechanism for obtaining the fluidic sample. Moreparticularly, the microfluidic timing mechanism may include a conduitthat may be a microfluidic channel 202 or a capillary tube. The conduitmay be partially filled with a timing fluid 201 (in other embodiments,the timing fluid may be without limitation, the external fluid thatenters from the isolated cavity 206, described in more detail below).Capillary trapped timing fluid 201 may initially be held in place withinthe microfluidic channel by, without limitation, surface tension. Themicrofluidic channel 202 leads to a timing cavity 204 that may be ofknown volume. The timing cavity 204 may initially be, withoutlimitation, empty.

Upon applying pressure to the timing fluid 201, the timing fluid 201advances within the microfluidic channel 202 into the timing cavity 204such that it causes a mechanical structure 205 to rupture (and/orcollapse) after a time delay. The mechanical structure 205 may beinsoluble in the environment or fluid in contact with the device. Themechanical structure 205 may be insoluble in water, bodily fluids, oil,oil field fluid, crude oil, salt water, or sea water, or combinationsthereof. The mechanical structure 205 may be made of an inorganicmaterial, a non-polymeric material, silicon, glass, or a ceramic, orcombinations thereof. As used in this description and the accompanyingclaims, the term “inorganic” shall have the meaning indicated, unlessthe context otherwise requires: a material composed of atoms ormolecules not containing carbon with, the exception of certain forms ofcarbon such as graphene, diamond, nanotubes and bucky-balls, which shallbe considered inorganic. Examples of inorganic materials include,without limitation, all metals, all types of glasses, silicon compoundssuch as oxides and nitrides, ceramic materials, silicon (in allcrystalline forms), quartz, diamond, sapphire, ruby, as well as allmaterials of geologic origin.

In accordance with various embodiments, the timing fluid may be routed,prior to entering the timing channel, through a trigger device that canenable or disable the passage of timing fluid as desired. The triggerdevice may be one of a check valve, an electrically-controlled solenoidvalve, a fluidic switch, or any other type of active valve known in theart. Examples of different types of valves used in microfluidic devicesare provided in “Components for integrated poly(dimethylsiloxane)microfluidic systems” Electrophoresis 2002, 23, 3461-3473; “Micro TotalAnalysis Systems: Latest Achievements” Anal. Chem. 2008, 80, 4403-4419,incorporated herein by reference in its entirety. The trigger device mayalso include a one-shot valve that initially blocks the passage oftiming fluid and upon receipt of an external signal permanently opensthe passage of timing fluid without requiring further power.

Prior to rupturing, the mechanical structure 205 isolates an isolatedcavity 206, which may include a sample chamber 209, from the externalenvironment, which may include an external fluid (which may be a gas).The mechanical structure 205 may be, without limitation, an isolationdiaphragm or isolation membrane that provides a barrier from theexternal environment. An example of a delayed actuator with avisco-elastic timer is described in U.S. Pat. No. 4,791,251 (Carter etal.), which is hereby incorporated by reference, in its entirety.

Illustratively, the timing fluid 201 entering the timing cavity 204 maycause a timing diaphragm 203 to deflect. A piercing structure, such as aprotrusion or other shaped structure on the timing diaphragm 203, maythen rupture or otherwise pierce the mechanical structure 205. Variousother membrane rupture mechanisms known in the art of microfluidicsystems, such as in systems used to provide drug encapsulation anddelivery, may be utilized (see, for example, M. Staples et al.: Pharm.Res., 23,847 (2006); J. T. Santini et al.: Angew. Chem. Int. Ed. 39,2396 (2000); J. H. Prescott et al.: Nat. Biotech. 24, 437 (2006), U.S.Pat. No. 7,455,667(B2), each of which is incorporated herein byreference in its entirety).

FIG. 2(b) shows the device 200 with the mechanical structure 205collapsed after applying pressure to the timing fluid 201 (and after thetime delay). The collapse of the mechanical structure 205 allowsexternal downhole fluid to enter a sample chamber 209 via an isolatedcavity/communication channel 206. The sample chamber 209 may bepre-vacuumed or hold a gas prior to deployment of the device 200. Aparticle filter may be placed within the isolated cavity/communicationchannel 206 to filter any contaminants. Note that prior to collapse ofthe mechanical structure 205, the isolated cavity/communication channel206 is typically inaccessible to the exterior environment. In otherembodiments, the mechanical structure 205 may allow partial/filteredaccess to the isolated cavity/communication channel 206 prior to itscollapse.

FIG. 2(c) shows the device 200 with the sample chamber 209 filled withsample fluid. An integrated one-way valve 207 (i.e., a check valve), mayassure sample isolation from the external environment. An example of amicro-fabricated one-way valve is described in the following documents:S. Beeby, G. Ensel, M. Kraft: MEMS Mechanical Sensors, Artech House,Boston Mass. (2004); and K. W. Oh et al.: J. Micromech. Microeng.,16,R13-R39 (2006), each of which is incorporated herein by reference inits entirety.

The timing mechanism, the sampling mechanism, and/or in variousembodiments, the entire device, may be electrically passive such that itdoes not include any powered electronic components (e.g., an electronicpower source, transmitter, amplifier etc . . . ). In variousembodiments, the timing mechanism, the sampling mechanism, and/or theentire device may be void of any active or passive electroniccomponents.

The passive microfluidic timing mechanism may be based, at least inpart, on the fact that the flow rate f of a Newtonian fluid through acapillary of roughly circular cross-section is proportional to thedifference in pressure ΔP between the ends of the capillary multipliedby the fourth power of the hydraulic radius R, and is inverselyproportional to the viscosity of the fluid η multiplied by the length ofthe capillary l: f=π·ΔP·R⁴/(8·η·l). In other embodiments, if thecapillary is chosen to have a rectangular cross-section with width w andheight h<w, the flow rate f can be calculated with the approximateformula: f=(1−0.63h/w)·ΔP·w·h³/(12·η·l). Such formulae may be found inthe literature, for example in the following documents: Stone, H.,Stroock, A., and Ajdari, A., “Engineering Flows in Small Devices,”Annual Review of Fluid Mechanics, Vol. 36, 2004, p. 381 and D. E.Angelescu: “Highly Integrated Microfluidics Design”, Artech House,Norwood Mass. USA (2011), each of which is incorporated herein byreference in its entirety.

If an empty cavity of known volume (i.e., the timing cavity 204) isseparated from a high-pressure fluid by a capillary of appropriategeometry, the time required to fill the timing cavity 204 can beaccurately determined from knowledge of device geometry, fluid viscosityand pressure differential. Assuming the timing fluid 201 has knowncharacteristics, and that the pressure/temperature history is recorded,the filling time of the timing cavity 204 can be fully determined bygeometrical device parameters such as timing cavity 204 volume,microfluidic channel 202 capillary diameter and length; the fourth powerdependence on diameter allows control of the fill-up time over severaldecades, resulting in a very versatile timing mechanism. A fullycharacterized timing fluid 201 may be used that advantageously may beimmiscible with both hydrocarbons and water. Examples of such timingfluids include, without limitation, various silicone oils andfluorinated solvents.

Alternatively, a non-Newtonian fluid with known rheological propertiescan be used as a timing fluid. In one embodiment, one may use ashear-thinning fluid as a timing fluid, which will result in a flowratewhich is very low at low pressures, but increases significantly once theambient pressure (and hence the shear stress in the microchannel)reaches a certain threshold value. In another embodiment, the timingfluid may be a visco-elastic fluid which behaves as an elastic body atlow shear stresses, thus completely blocking flow at low pressures. Asthe pressure reaches a threshold value (corresponding to the yieldstress of the timing fluid), the timing fluid will start flowing. Thisembodiment allows the passive timing devices described above to beinactive below a certain threshold pressure, thus allowing prolongedstorage at a pressure situated below the threshold pressure.

FIG. 2(d) shows the device 200 ready to be interrogated after surfaceretrieval. The sample fluid stored in the sample chamber 209 remainsisolated from the environment by the one-way valve 207, so that variousphysical and chemical property measurements can be obtained. A sensor208 may be positioned within, or otherwise operationally coupled to, thesample chamber 209 and/or isolated cavity 206, so as to provide variousindications or measurements associated with the sample fluid. In variousembodiments, a microelectromechanical sensor (MEMS) design may providehermetic encapsulation of sensor components within, for example, thesample chamber 209. The sensor 208 may include a material thatchemically reacts with the fluid, and/or an electrode allowing anelectrochemical measurement to be performed on the fluid sample.

The above-described timing mechanism in conjunction with passiveactuators may thus be used to deploy self-triggering sample acquisitiondevices/vessels. For deployment within a rock matrix, such devices maybe density-matched to an injection fluid by incorporating vacuumcavities of appropriate dimensions, which will facilitate passivedeployment by injection as well as device retrieval.

Acoustic Emission and Triangulation

The above-described device for sample acquisition may be used togenerate acoustic signals. For example, in various embodiments thetiming mechanism may trigger the piercing of multiple mechanicalstructures/isolation diaphragms, possibly in sequence. For example, ifthe cavity behind each isolation diaphragm has volume V (initially undervacuum), upon piercing, these cavities will suddenly collapse and/orrupture, and fill with reservoir fluid at the ambient hydrostaticpressure. The filling of the empty cavity 301 may be very sudden, andwill emit a very short burst of acoustic energy 303, as shown in FIG.3(a), in accordance with an embodiment of the invention. Laboratorystudies of collapsing bubbles have been performed by others (forexample, A. VOGEL, W. LAUTERBORN, R. TIMIM: “Optical and acousticinvestigations of the dynamics of laser-produced cavitation bubbles neara solid boundary”, J. Fluid Mech., Vol. 206, pp. 299-338 (1989), whichis incorporated herein by reference in its entirety), proving that themajority of the bubble energy is emitted into the acoustic transients.The total amount of energy that may be released by sudden filling of acavity may be roughly estimated as E=pV, where p is the reservoirpressure. For an exemplary volume of 1 mm³ and an ambient pressure of1000 Bar (app. 14500 psi), this corresponds, without limitation, to anemission energy of 100 mJ in a time interval of approximately a fractionof a thousandth of a second to a few thousandths of a second. Thiscorresponds to an acoustic power of over 10-1000 W during each collapseevent. Such acoustic emission can then be detected and recorded usingremote microphones, hydrophones, geophones, accelerometers or othertypes of sensors or recorders.

The timing mechanism may trigger several acoustic events in sequence,with the time delay between consecutive collapses defined by thegeometry of the associated microfluidic channel and timing cavity. Eachdevice and/or sampling mechanism may be built with a different timingsequence, or with different geometrical parameters, to provide a uniqueacoustic signature. Such devices may also be realized without a samplingcavity, with the sole purpose of emitting a sound at a time determinedby the microfluidic timing mechanism.

The acoustic emission for each collapse event will create an acousticwavefront 303 which will propagate through the fluid and the surroundingrock matrix. The velocity of the wavefront will typically be equal tothe sound velocity in the fluid, or in the rock matrix. By placingmultiple microphones 305 at different positions in the formation, asshown, for example, in FIG. 3(b), the arrival time of the wavefronts ateach microphone 305 may be determined. Based on the time delays betweenthe arrival of the acoustic signal at the different microphones,combined with a knowledge or an educated estimation of the soundvelocity in the medium, the position of the smart vessel can then bedetermined, using, without limitation, triangulation, similar to anunderground GPS system, or using compressional/shear signal processing.The time of the sample acquisition may also be recorded. It is notedthat FIG. 3(b) is by no way limited to the shown configuration ofmicrophones or devices. In other embodiments of this invention,additional microphones may be located on the ground around the well, orat other subterranean locations, such as in a nearby well 306, cavities,or holes.

Usage as Vehicle for Time-Release of Particles, Chemical Products, orPharmaceutical Products

The above-described devices may be used as vehicles for transport andtime-release of, without limitation, micro- and nano-particles, chemicaland/or pharmaceutical products, by including the products or particleswithin the isolated cavity and/or sampling chamber separated by themechanical structure (e.g., isolation diaphragm). The timing mechanismmay trigger the piercing of the isolation diaphragm after a time delayas described above, at which point the fluid surrounding the devicepenetrates within the cavity behind the isolation diaphragm and comes incontact with the particles, chemical and/or pharmaceutical products. Theparticles or products may then dissolve within, or mix with the fluidsurrounding the device, thus releasing said particles or chemical orpharmaceutical products into the surrounding environment.

Said particles or chemical products or pharmaceutical products mayinclude, without limitation, chemicals for sanitizing water or otherfluids; fluorescent chemicals that may be used as flow tracers; variouschemical reagents and chemical cleaning agents; pharmaceutical productssuch as medications or drugs; various types of nutrients; micro- ornano-particles to be used as flow tracers; materials that react in anaggressive way with the environment, such as by producing an explosionor a rapid release of energy; and/or chemically-functionalized micro-and nano-particles which can react to some environmental parameter.

In accordance with an embodiment of the invention, a passive timingdevice such as the one previously described may be injected into ageological formation or in a hydraulic fracture by means of pumping viaan injection well. When the timing mechanism triggers the piercing ofthe isolation membrane, functionalized nanoparticles are released withinthe geological formation as described above. The nanoparticles reactwith the local environment, are carried by flow towards the injectionwell, and are retrieved from the well at the surface. The nanoparticlesize may be chosen to be substantially smaller than the average porethroat diameter, which will insure that the particle will be transportedby flow within the geological formation without clogging the pores. Byanalyzing the particles after retrieval at the surface, one will be ableto infer information about the environment within the geologicalformation at the time of nanoparticle release. By injecting multiplesuch passive timing devices which are triggered at different times, onemay be able to continuously monitor one or several parameters atmultiple remote locations within the geological formation, which may beotherwise inaccessible.

FIG. 4 shows a passive timing device 404 that includes, withoutlimitation, a pharmaceutical product 403 that is released within a humanbody 405, in accordance with an embodiment of the invention. Theisolation diaphragm(s) is pierced at times set by the passive timingdevice, whereupon the corresponding pharmaceutical products 403positioned, without limitation, within the isolated cavity and/orsampling chamber, are released within the human body. Multiple deviceswith one or more diaphragms may be utilized. Using such a system,complete treatment plans may be delivered without any activeintervention, by adjusting the timing parameters and the types andquantities of pharmaceutical products within each cavity.

The device 404 may be attached to the skin of the human body 405, or maybe implanted within the body. An external source of pressure, or anexternal pump, may be used to drive the timing fluid within the timingcavity of the device 404. In one embodiment, such external source ofpressure may be, without limitation, a pressurized gas cartridge.

FIG. 5 shows a passive timing device that includes a filter 502 forcontaining the broken diaphragm particles, in accordance with anembodiment of the invention. Upon piercing of the mechanical structure(e.g., isolation diaphragm), the filter 502 advantageously prevents thebroken diaphragm particles from passing into the external fluid, whilestill allowing, for example, a pharmaceutical product 501 to freely passthrough. This embodiment may be particularly important if the passivetiming device is going to be included within a human body.

Tool Implementation

The above-described devices may also be integrated within downholesampling and measurements tools, such as the Modular Formation DynamicsTester (MDT) produced by Schlumberger, the Formation Multi-Tester (FMT)produced by Baker Hughes or the Sequential Formation Tester (SQT)produced by Halliburton, or any other similar tool. Arrays of thesampling devices, integrating a plurality of devices and/or samplingmechanisms on a single microfabricated substrate, may be incorporatedwithin the tool architecture. The above-described devices may also beintegrated in production logging oilfield tools, possibly in slicklinetools.

FIG. 6 shows integration of a plurality of sampling devices and/ormechanisms 605 within an oilfield-sampling tool such as a MDT, a FMT ora SFT, in accordance with an embodiment of the invention. The tool 600pushes a pad 603 into the geological formation wall, and pumps theformation fluid into an internal flow-line 601, where the fluid comesinto contact with a smart sampling device array 605. Each device 607 mayacquire a sample, perform a measurement, and/or emit an acoustic signalwhich is recorded by a microphone within the tool. The recorded acousticsignals may provide, for example, the precise time when each measurementwas performed and may uniquely identify the device which performed themeasurement.

The device 607 may come into contact with the formation fluid as it ispumped into the tool flowline 601. The acoustic emission events may berecorded using a microphone implemented in the tool, and later analyzedat the surface to infer the precise time of sample acquisition for eachof the smart vessels in the array, thus providing very valuabletime-series data.

FIG. 7 shows another embodiment of the invention, where an array ofsmart sampling devices is embedded within a submarine measurement system701, which may be attached with a cable 702 to, without limitation,either a buoy, a rig, a submarine, a vessel or a ship 700. Themeasurement system 701 may either be positioned in a stationary mannerin the body of water 703, at a depth dependent, without limitation, onthe length of the cable 702, or it may be dragged through the body ofwater by the ship 700. The smart sampling devices in the measurementsystem 701 perform sample acquisitions and measurements at timesdetermined by their respective timing mechanisms, thus providing atime-series or a spatial map of measurements at a given depth.

Viscosity Measurement

FIG. 8A shows a viscosity measurement system that may be fully passive,in accordance with an embodiment of the invention. The system 801illustratively includes two devices 805 and 806 connected together inseries, in such a way that the first device's isolated cavity 802 isconnected, via a conduit, such as a microfluidic channel or other typeof tube of controlled dimension 803, to the timing cavity 804 of thesecond device. After the rupture or collapse of the first device'smechanical structure 807, the second device's timing cavity 804 willstart filling with external fluid 808. The filling time of the seconddevice's timing cavity 804, and the corresponding rupture or collapse ofthe second device's mechanical structure 809, may depend, at least inpart, on the geometry of the conduit 803, on external pressure, and/oron the viscosity of the external fluid 808. By controlling, for example,the geometrical parameters, and by measuring external pressure, one canrelate the viscosity of the external fluid to the time measured betweenthe rupture or collapse of the first sampling device's mechanicalstructure 807 and that of the second device's mechanical structure 809.This allows an accurate viscosity measurement to be performed on theexternal fluid.

More particularly, providing that the conduit 803 has hydrodynamicresistance Rh, the external fluid has pressure P, and the timing cavity804 has volume V, the filling time t of cavity 804 will be given byt=Rh×V/P. The hydrodynamic resistance of a circular channel of radius Rand length L is given by Rh=8×n×L/(π×R⁴). The hydrodynamic resistance,for a rectangular conduit of lateral dimension h<w and length L, can beapproximated as Rh=12×n×L/(h³×w×(1−0.63×h/w)), where n is the viscosityof the external fluid (see, for example, D. Angelescu “Highly IntegratedMicrofluidics Design”, Artech House 2011). By measuring the filling timeof the cavity 804, therefore, one can infer the value of thehydrodynamic resistance of the conduit 803, and knowledge of thegeometrical details of this conduit allows a determination of the fluidviscosity n from the above formulas: n=t×P×π×R⁴/(8×L×V) for a circularconduit, and, respectively, n=t×P×h³×w×(1−0.63×h/w)/(12×L×V) for arectangular conduit.

In accordance with further related embodiments, theviscosity-measurement device described in the above paragraph mayincorporate means of controlling and/or measuring the external fluidpressure, and of recording the time between the collapse of the firstdevice's and the second device's mechanical structures 807 and 809. Thecollapse of a device's mechanical structure may be detected acoustically(by detecting the acoustic signature emitted during the collapse),electrically (by recording a disruption to an electrical circuit causedby the collapse), or optically (by observing the collapse using acamera, or another type of optical system), or by any other means knownto a person skilled in the art.

FIG. 8B shows another embodiment of the viscosity-measurement deviceincorporating an additional device 810 connected in series with devices805 and 806 in such a way that the isolated cavity of device 806 isconnected to the timing cavity of the device 810 by a second conduit 811of controlled geometry. This second conduit 811 may have differentcross-section and length from the first conduit 803, thus resulting in adifferent timing fluid flowrate into the timing cavity 812 of the device810.

This difference in geometry between conduits 803 and 811 may be used toextend the measurement range of a device and measure different ranges offluid viscosity using the viscosity-measurement device. In oneembodiment, the geometry of conduit 811 may be chosen so that thefilling time of cavity 812 is much longer than the filling time ofcavity 804 (in case we assume equal volumes for the timing cavities 804and 812, this corresponds to the conduit 811 having significantly higherhydrodynamic resistance than conduit 803). If viscosity of the externalfluid is very low, and the filling time of the cavity 804 is too shortto enable an accurate measurement, then a much more accurate measurementof viscosity may be obtained by using the filling time of cavity 811. Onthe other hand, for highly viscous fluids, the filling time of cavity804 may provide a reasonably accurate measurement, such that waiting forthe filling of cavity 811 may no longer be necessary. Additional devicesmay be connected in series, with conduits connecting the isolated cavityof one device to the timing cavity of the next, to further extend therange of accurate viscosity measurements.

Manifold Sampling and Chemical/Biochemical Measurement Device

FIG. 9A shows a sampling and measurement system 901 that includesmultiple devices 902, 903 connected, via a manifold 904, to an externalsampling conduit 905, in accordance with an embodiment of the invention.Upon a new sample being acquired by one of the devices, new fluid may bedrawn through the sampling conduit 905. The sampling chambers 906, 907for the devices 902, 903 may be designed with volumes such that the deadvolumes within the system, the internal volume of the conduit 905 or thevolume of the connecting manifold 904 be negligible in comparison to thevolume of the sampling chambers 906, 907.

The sampling conduit 905 may be connected to a pipe, a fluid reservoir,or another external fluid supply 908 that needs monitoring. Each time anew sample is acquired by one of the devices 902, 903, the respectivevolume of fluid is drawn from the said fluid supply 908, through theconduit 905 and manifold 904, into the sampling chamber of the activedevice.

Each sampling chamber 906, 907 may be, without limitation, a vial, abottle and/or another leakproof container/receptacle. One or moresampling chambers 906, 907 may include a pre-measured amount of chemicalor biological reagent 909, or a combination of several such reagents 910in liquid, solid, powder or lyophilized form, in free form orimmobilized on a solid substrate. Upon sample entering the samplingchamber 906, 907, a sequence of chemical or biological reactions occurbetween the sample and the said reagents. Different sampling chambers906, 907 within the same system may contain different reagents 909, 910.

In various embodiments of the invention, said chemical or biologicalreactions may have a visible outcome. For example, the coloration of thesolution or of an immobilized reagent may change, there may be a changein turbidity, there may be a development of fluorescence, or anycombination of the above.

The visible outcome may be recorded in-situ, by performing an opticalmeasurement via, without limitation, the vial wall or via an opticalwindow 911 embedded in the sampling chamber 907. The optical measurementmay include, without limitation, acquiring an image of the samplingchamber using an external optical instrument 912 such as color or blackand white camera, a spectrophotometer, a fluorescence detection device,a Raman scattering device, and/or a turbidity measurement device.

FIG. 9B shows an external sampling conduit connected, via a T-junction913, to a reagent reservoir 914, in accordance with an embodiment of theinvention. The reagent reservoir 914 may be substantially at the samepressure as the fluid being sampled. For example, and withoutlimitation, the reagent reservoir 914 may be a bladder submerged intothe external fluid being sampled, or an accumulator. A fluidicresistance 915 may be included between the reagent reservoir 914 and theT-junction 913, such as to limit the flow rate of reagent. Each time asample is drawn in, a proportional amount of reagent is drawn in alongwith the sample, the mixing ratio being set passively by the saidfluidic resistance.

The external sampling conduit may include a micromixer 916 downstreamfrom the T-junction 906, 907, such that the combined sample and reagentstream is thoroughly mixed after passing through the micromixer 916.

In various embodiments of the invention, the external sampling conduitmay include a microfluidic sensor 917, such that each time a sample isacquired by one of the devices, the microfluidic sensor 917 performs ameasurement on the fresh stream of fluid. The measurement may include,without limitation, an optical measurement (e.g., index of refraction,absorbance, fluorescence), an electrical measurement (e.g.,conductivity, resistivity, dielectric constant), an electrochemicalmeasurement (e.g., ionic content, chemical composition), a physicalmeasurement (e.g., viscosity, density), a chemical measurement (chemicalcomposition), and/or biological measurement (cell count).

Preconcentration and/or Sample Filtering

FIG. 10A shows a device 1001 that may be used to sample from an externalfluid contaminated with one or a combination of particles 1003, organicpollutants, biological pollutants, chemical pollutants, plankton,phytoplankton, nuclear matter, volatile organic compounds,pharmaceutical matter, or other contaminants, in accordance with anembodiment of the invention. The device 1001 includes one or moreintegrated filters 1002 that the sample has to come in contact with,upon or prior to entering the sampling chamber 1004. The filter 1002 mayinclude, without limitation, one or a combination of the following: amechanical filter, a solid phase extraction column, a packed column, ahydrocarbon filter, a gas chromatography preconcentrator, a filter tocollect and concentrate radioactive material, a biological filter, anabsorbent medium, a scavenging medium, a hydrophobic material and ahydrophilic material.

FIG. 10B shows the device 1001 after sampling, the filter 1002 havingcollected different components present in the fluid sample, such as,without limitation: particles 1003, organic pollutants, biologicalpollutants, chemical pollutants, plankton, phytoplankton, nuclearmatter, volatile organic compounds, pharmaceutical matter, or othercontaminants.

The filter 1002 may, optionally, be later retrieved and analyzed, toprovide time-series data concerning the contaminant of interest at thelocation of the device. Analyzing the filter 1002 may requirebackflushing, thermal desorption or solvent washing, and/or othertechniques to remove the adsorbed, absorbed, or trapped contaminants.Analysis may require analytical techniques such as, without limitation,GC/MS, HPLC, gamma ray spectroscopy. In various embodiments, the filtersmay be analyzed in-situ.

Maintaining Sample Integrity by Controlled Sampling and High-PressurePreservation

FIGS. 11A-C shows a system 1101 capable of acquiring a sample from anexternal fluid 1102, pressurizing it at a pressure higher than thepressure of the external fluid, and maintaining it at such pressure forextended periods of time, in accordance with an embodiment of theinvention. Such a system 1101 advantageously may ensure that the samplewill remain in single-phase configuration and will not undergo athermodynamic transition to a multi-phase fluid. This is particularlyimportant when sampling hydrocarbon fluid from a geological formationduring oilfield drilling, wireline logging, or production operations,since the sample needs to remain in single phase throughout thetransport to the analysis laboratory.

The system 1101 shown in FIG. 11A includes a sampling chamber 1104divided into a first portion and a second portion, in accordance with anembodiment of the invention. The isolated cavity of a first device 1103is connected via a conduit to the first portion of the sampling chamber1104. The second portion of the sampling chamber 1104 is connected via aconduit 1107 to an isolated cavity 1106 of a second device 1105. Themechanical structure 1111 of the second device 1105 may be, withoutlimitation, scheduled to open at a later time relative to the mechanicalstructure 1110 of the first device 1103. The first portion of thesampling chamber 1104 may be separated from the external fluid by afirst check valve 1108, allowing fluid to enter the sampling chamber1104 but not to leave it. The connection between the two portions of thesample chamber 1104 may include a second check valve allowing flow fromthe second portion of the sampling chamber 1104 to the first portion ofthe sampling chamber 1104, but preventing flow in the oppositedirection. The first and second portions of the sampling chamber 1104may be separated by, without limitation, a leakproof piston 1109 or aflexible membrane, allowing for the pressures in the first and secondportions to be equalized without requiring physical contact of thefluids in the two portions. The mechanical structure 1110 of the firstdevice 1103 may be connected to the fluid to be sampled 1102, with themechanical structure 1111 of the second device 1105 connected to apressurized fluid reservoir 1112 at a pressure that is higher than theexternal pressure. The pressurized fluid reservoir 1112 may incorporate,without limitation, an accumulator, a pressurized gas container, and/ora mechanical spring.

FIG. 11B shows the system 1101 with the timing fluid cavity 1113 of thefirst device 1103 filled with timing fluid, causing the rupture orcollapse of the first device's mechanical structure 1110, and allowingthe external fluid 1102 to enter the first portion of the samplingchamber 1104.

FIG. 11C shows the subsequent rupture or collapse of the second device'smechanical structure 1114, the fluid from the pressurized reservoir 1112entering the second portion of the sampling chamber 1106 and applyingits pressure, via the piston 1109, to the sample contained in the firstportion of the sampling chamber 1104. The fluid in the first portion ofthe sampling chamber 1106 is prevented from leaving the chamber by thecheck valve 1108, and therefore is maintained at a pressure higher thanthe pressure at which it was acquired.

FIG. 12A shows a device 1201 for performing a sampling operation from ahigh-pressure external fluid 1202 without significantly lowering thepressure of the external fluid during the sampling process (without“shocking” the fluid), in accordance with an embodiment of theinvention. The sampling chamber 1203 may include a leak-proof piston1204 or flexible membrane that separates it into a first portion 1205and a second portion 1206. The second portion 1206, which is fartheraway from the mechanical structure 1210 may be pre-filled with asecondary liquid 1207 and is connected, via a conduit 1208, such as amicrofluidic channel and/or fluidic constriction, to another auxiliarychamber 1209. The conduit 1208 may include a check valve 1212 orbackpressure regulator that assures that the fluid 1207 does not leakfrom the second portion 1206 to chamber 1209 prior to sampleacquisition. Upon the collapse of the mechanical structure 1210, thesample enters the first portion 1205 of sampling chamber 1203 andapplies pressure to the piston 1204, which moves at a slow ratecontrolled, for example, by the viscosity of the secondary liquid 1207and the geometry of the conduit 1208.

In another related embodiment, the auxiliary chamber 1209 may bepre-filled with pressurized gas. Upon sample acquisition, the gas iscompressed, forming a cushion that will keep the secondary liquid 1207,and consequently the sample, pressurized. The sample in the firstportion 1205 of the sampling chamber 1203 is prevented from leaving bythe check valve 1211, and therefore is maintained at a pressure that iscomparable to the pressure at which it was acquired.

In another related embodiment, the sampling chamber may include acompressed spring and a piston, one side of the piston in contact withthe sampling chamber and the other side in contact with the externalfluid, such that prior to sampling being initiated the spring iscompressed by the piston due to external fluid pressure being applied tothe piston. Upon sampling being initiated, the hydrostatic pressure onboth sides of the piston equalizes and the elastic force of the springdisplaces the piston, thus acquiring a sample at controlled speed andwith minimal change to the overall submerged weight and buoyancy of thedevice. The travel of the piston may be restricted due to the presenceof a mechanical fixture such as a stop or a ridge.

FIG. 12B displays another embodiment of FIG. 12A that in addition toallowing a sampling operation to be performed from a high-pressure fluidwithout dropping the pressure of the fluid or otherwise “shocking” itduring the sampling, also allows the sample to be maintained at a highpressure after sampling, possibly higher than the initial external fluidpressure, thus preventing phase separation. In addition to the detailsprovided above with regard to FIG. 12A (the numbering of which will bemaintained), in the system 1213 the second portion 1206 of the samplingchamber 1203 that is farther away from the mechanical structure 1210 isalso connected via a conduit 1215 to an isolated cavity 1216 of a seconddevice, which is scheduled to open at a later time. The conduit 1215 mayinclude a check valve 1214 allowing flow from the isolated cavity 1216to the second portion 1206 of the sampling chamber 1203, but preventingflow in the opposite direction. Positioned between the first portion1205 and the second portion 1206 of the sampling chamber 1203 may be apiston or a flexible membrane allowing for the pressures to be equalizedwithout requiring physical contact of the fluids in the two portions1205 and 1206. The mechanical structure 1210 of the first device isconnected to the fluid to be sampled 1202, whereas the mechanicalstructure 1217 of the second device is connected to a pressurized fluidreservoir 1218 at a pressure that is higher than the external pressure.The pressurized fluid reservoir 1218 may incorporate, withoutlimitation, an accumulator, a pressurized gas container, and/or amechanical spring. Upon the rupture or collapse of the first device'smechanical structure 1210, external fluid 1202 is allowed to enter thefirst portion 1205 of the sampling chamber 1203, at a slow rate that iscontrolled, at least in part, by the viscosity of the secondary liquid1207 and/or the geometry of the conduit 1208. Upon the subsequentrupture or collapse of the second device's mechanical structure 1217,the fluid from the pressurized reservoir 1218 enters the second portion1206 of the sampling chamber, and applies its pressure to the piston1204, and consequently to the sample contained in the first portion 1205of the sampling chamber 1203. The fluid in the first portion 1205 of thesampling chamber 1203 is prevented from leaving the check valve 1211,and therefore is maintained at a pressure higher than the pressure atwhich it was acquired.

Complex Sample Manipulations, Filter Backflushing, and Transfer BetweenVials

FIGS. 13A-D show, in chronological order, operations performed by asystem that, in addition to sampling at a time controlled by a passivetiming mechanism, integrates a mechanism allowing the subsequenttransfer of the sample from an initial sampling chamber to anothersampling chamber after a given amount of time, in accordance with anembodiment of the invention. This operation can be further repeated asdesired. The system described in FIGS. 13A-D may also integratedifferent chemical or biochemical reagents in each of the samplingchambers, and/or may integrate a filtration medium that can bebackflushed as part of the sample transfer to another sampling chamber,thus concentrating certain components of the sample.

FIG. 13A shows a system 1306 that includes multiple sampling devices1301, 1302, 1303, such that a sample from external fluid 1304 may beacquired by a first device 1301 and provided to a first portion of asampling chamber 1305. The first portion of sampling chamber 1305 mayoptionally include a filter 1307. The first portion of the samplingchamber 1305 may also integrate an optional first group of chemical orbiochemical reagents. The first portion of the sampling chamber 1305 maybe separated from a second portion of the sampling chamber 1305 by apiston, or a flexible member membrane. The second portion of thesampling chamber 1305 is in fluidic communication with an isolatedcavity 1308 of a second device 1302 that is scheduled to open at a latertime. The first portion of the sampling chamber 1305 is also connected,upstream of the optional filter 1307, to the mechanical structure 1312of a third device 1303 that is scheduled to open after the second device1302. The mechanical structure 1313 of the second device 1302 is in turnconnected to a pressurized fluid reservoir 1314, such as, withoutlimitation, a pressurized gas reservoir, or an accumulator.

FIG. 13B shows the system 1306 after the collapse of the first device'smechanical structure 1309, showing a sample 1310 being acquired into thefirst portion of the sample chamber 1305, mixing with the optional firstreagent of group of reagents, and pushing the piston 1311 into a farposition distal the first device's mechanical structure 1309.

FIG. 13C shows the system 1306 after the later collapse of the seconddevice's 1302 mechanical structure 1313. The pressurized fluid fromreservoir 1314 enters the second device 1302 and applies its pressure tothe backside of the piston 1311. The sample acquired in the firstportion of the sampling chamber 1305 cannot backflow into the firstdevice 1301 due to the check valve 1315.

FIG. 13D shows the system 1306 after the later collapse of the thirdmechanical structure 1312. The sample 1310 contained in the firstportion of the sampling chamber 1305 is pushed, by the pressure of thepressurized gas reservoir 1314, into the sampling chamber 1315 of thethird device 1303. During this process, the sample is forced to traversethe optional filter 1307 in reverse, thus back-flushing it andtransporting the filtered material into the sampling chamber 1315 of thethird device 1303. By choosing the volumes of the sample chamber 1315 ofthe third device 1303 to be lower than the volume of the first portionof sample chamber 1305, a higher concentration of the componentsfiltered from sample 1310 can be obtained in the sampling chamber 1315.The sample chamber 1315 of the third device 1303 may also include anoptional second group of chemical or biochemical reagents, such that thesample 1310, after having already reacted with the optional first groupof reagents present in the first portion of the sample chamber 1305, nowhas to react with the optional second group of reagents. The process maybe repeated multiple times.

FIG. 13E shows the above-described system 1306 slightly modified, withthe sampling chamber 1305 further including a first reservoir 1316 thatmay be pre-filled with a liquid solution 1317, and a second reservoir1318 that initially may be empty. The first reservoir 1316 may beseparated using a piston 1319 or flexible membrane, or a similarstructure, from the second portion of the sampling chamber 1305 that isin fluidic communication with the isolated cavity 1308 of the secondsampling device 1302. Optionally, one-way check valves 1320, 1321 may beintegrated allowing the fluid to circulate from the filter 1307 into thesecond reservoir 1318, and, respectively, from the first reservoir 1316towards the filter 1307. Upon the sample acquisition by the first device1301, the sample moves through the filter 1307 into the second reservoir1318. Upon the collapse of the mechanical structure 1313 of the seconddevice 1302, pressure from pressurized reservoir 1314 is applied to theliquid solution 1317 in the first reservoir 1316. As the mechanicalstructure 1312 of the third device 1303 collapses, the liquid solution1317 is forced through the filter 1307, and transports the materialcollected on filter 1307 into the sampling chamber 1315 of the thirddevice 1303. Optionally, a first and a second group of reagents may beincorporated in the first portion of the sampling chamber 1305, and,respectively, in the sampling chamber 1315 of the third device 1303.Additional reagents may be included in the liquid solution 1317 presentin the first reservoir 1316.

The operation mode described above allows complex sample preparation,such as, without limitation, mixing with multiple chemical orbiochemical reagents, backflushing using a specific liquid solution thatis different from the original sample liquid, pre-concentration in aseparate vial, and additional chemical and/or biochemical reactions onthe preconcentrated sample.

Daisy Chain Configuration of Multiple Sampling Systems

FIG. 14 shows multiple systems connected in a “Daisy-chain”configuration, in accordance with an embodiment of the invention. Uponone system acquiring its last sample it automatically triggers the startof sampling using the next system in the daisy chain. This mode ofoperation can allow an unlimited number of systems to be connected, andthus extends the sample acquisition capacity of the combined systembeyond the limits of any single individual system connected in the daisychain.

Two systems 1401 and 1402, each including a plurality of devices 1403and 1404, and 1405 and 1406, respectively, are timed to acquirecorresponding samples at different times. Illustratively, the mechanicalstructure 1407 of the last device 1404 of the first system 1401 may beconnected to the timing fluid reservoir 1408 of the second system 1402.Additionally, the isolated cavity 1409 of the last device 1404 of thefirst system 1401 may be connected to the timing mechanism of one ormore of the devices 1405, 1406 associated with the second system 1402.In this configuration, the collapse or rupture of the mechanicalstructure 1407 of the last sampling device 1404 of the first system 1401triggers the start of the sampling using the second system 1402, thusallowing the systems to be connected in a daisy-chain configuration.

External Control of the Sampling Time

FIG. 15 shows a system 1501 capable of controlling the sampling times ofa plurality of sampling devices 1503 and 1504 using a trigger device1505 that may be in the form of a fluid control device. The triggerdevice 1505 may be placed, without limitation, on a timing fluid line1506, between an optional pressurized timing fluid reservoir 1507 andthe timing channels 1508, 1509 of any number of the multiple timingdevices 1503, 1504 associated with the system 1501. The trigger devicemay be controlled by a control unit 1510 that may either be a subsystemof system 1501, or an external, possibly remote, system.

The pressurized timing fluid reservoir 1507 may be absent, instead thetiming fluid may be maintained at a pressure equal to the external fluidbeing sampled. The trigger device 1505 can be any type of device thatcan enable or disable the passage of timing fluid as desired. Thetrigger device 1505 may be one of a check valve, anelectrically-controlled solenoid valve, a fluidic switch, or any othertype of active valve known in the art. The trigger device 1505 may alsoinclude a one-shot valve, that initially blocks the passage of timingfluid, and upon receipt of an external signal from the control unit 1510permanently opens the passage of timing fluid without requiring furtherpower.

In accordance with further embodiments, the system 1501 may incorporatea recording mechanism that records that a sample has been acquired,and/or of transmitting this information to either an external system, tothe control unit 1510, or both. The collapse or rupture of themechanical structure and the subsequent sample acquisition may bedetected acoustically (by detecting the acoustic signature emittedduring the collapse), electrically (by recording a disruption to anelectrical circuit caused by the collapse), optically (by observing thecollapse using a camera, or another type of optical system, or byobserving an optical change to a vial being filled with fluid), or byany other means known in the art.

Passive Timing and Sample Acquisition Implemented Using a PistonAssembly

In certain applications, using a timing diaphragm inside a samplingmechanism may not be convenient or ideal. Instead it may be advantageousto use a different type of moving part that is capable of achieving agood fluidic seal.

FIGS. 16A and 16B show a sampling device 1600 that is configured toacquire a sample from an external fluid 1601, in accordance with anembodiment of the invention. The sampling device 1600 includes amechanical structure 1602 that is in contact with the external fluid1601. The sampling device 1600 further includes an isolated cavity 1611.A piston 1604 is positioned, without limitation, within the isolatedcavity 1611, and is configured to move within said cavity 1611. Invarious embodiments, the piston 1604 separates said cavity 1611 into twoportions that are not in fluid communications because of a sliding seal1605. The sliding seal 1605 may be, for example, an o-ring or any othertype of seal known in the art that performs a sealing function whileallowing the piston 1604 to slide. The sampling device 1600 may furtherinclude a timing cavity 1616 in fluid communication with one side of thepiston.

The sampling mechanism may further include a conduit 1615 that may be,without limitation, a microfluidic channel or a capillary tube, and thatmay have a predefined geometry. Upon applying pressure to the timingfluid 1609 (which may be a liquid or a gas), said timing fluid 1609flows within the conduit 1615 at a rate, for example, that may bedictated by the applied pressure, the predefined channel geometry andknown timing fluid properties. Upon reaching the timing cavity 1611 andfilling it after a timing interval, the timing fluid 1609 appliespressure to one side of the piston 1604, which advances within theisolated cavity 1611 (alternatively called a piston cavity).

The piston 1604 may also include a piercing structure, such as aprotrusion 1603, which may be, without limitation, in the form of aneedle, a pin, a raised boss, or any other type of structure known inthe art. The protrusion 1603 may be separate from the piston 1604 or anintegral part of it. Upon the piston 1604 sliding far enough into theisolated cavity 1611, the protrusion 1603 contacts the mechanicalstructure 1602 and transmits and/or concentrates mechanical stress ontothe mechanical structure 1602.

Under the effect of said stress, the mechanical structure 1602 ispierced and the mechanical structure 1602 is destroyed, such as by,without limitation, rupturing or by collapsing, allowing the externalfluid 1601 to enter the isolated cavity 1611, which may then furtherlead to a sampling chamber 1607. The isolated cavity 1611 and thesampling chamber 1607 may be part of the same assembly as the samplingmechanisms, or they may be separate parts that are connected using someform of fluidic or mechanical fixture known to the person skilled in theart, such as a tube, a channel, or a pipe 1608. Prior to entering thesampling chamber 1607, the external fluid 1601 may pass through a checkvalve 1606 that allows fluid to flow into the sampling chamber 1607 butprevents the fluid 1601 from flowing in the opposite direction.

The timing fluid 1609 may further be in fluidic communication via,without limitation, a tube 1610, a channel, or a pipe, or any other typeof fixture or device, that allows fluidic communication with apressurized timing fluid reservoir 1613. In some embodiments, the timingfluid reservoir 1613 may be at a pressure that is equalized with thepressure of the external fluid 1601. In other embodiments, the timingfluid 1609 may be the same fluid as the external fluid 1601. The tube1610 may be optionally connected to an on/off valve 1612, which may bemanually operated or controlled by an optional control device 1614.

The control device 1614 and the valve 1612 may be electrically active.The control device 1614 may be triggered remotely. The triggering actionin itself may be transmitted to said control device 1614 via amechanical, acoustical, electrical or electromagnetic wired or wirelesslink. For example, the triggering action may be transmitted to thecontrol device 1614 using, without limitation, a mechanical cable orlever, a serial communication cable, a parallel communication cable, anelectrical triggering cable, an electromagnetic wave using a mobiletelephony network or a radio frequency or satellite connection, apressure wave such as an acoustic or sound wave using an acoustic module(such as sonar and/or a hydrophone, a speaker and a microphone, orsimilar), or any other form of acoustic, electrical, electromagnetic,acoustic or mechanical communication and/or triggers known in the art.

FIG. 16B shows the sampling device 1600, after the piston 1604 has movedunder the effect of pressure from the timing fluid 1609, and theprotrusion 1603 of the piston 1604 has pierced the mechanical structure1602. Sample chamber 1607 is shown filled with external fluid 1601.

Triggered Sampling Implementation with Different Passive TimingDurations

FIG. 17 shows a configuration of a sampling device 1700 that allows saidsampling device 1700 to be in a stand-by mode for an extended period oftime, and then, upon receiving an external trigger, to initiate anelectrically passive timing operation and to acquire a sample fromexternal fluid 1708 after said electrically passive timing operation isperformed, in accordance with an embodiment of the invention. The device1700 includes a timing diaphragm 1701, and a mechanical structure 1702initially in contact with the external fluid 1708 and separating it froman isolated cavity 1713. The mechanical structure 1702 may be piercedand consequently destroyed (such as by collapsing or rupturing) by theaction of the timing diaphragm 1701. The device may further include aconduit 1704, such as, without limitation, a channel, a tube, amicrofluidic channel, or a pipe, and a timing cavity 1703.

The conduit 1704 is in fluidic communication with a pressurized timingfluid reservoir 1710, and may optionally include an on/off valve 1709.The valve 1709 may be actuated manually, or remotely by an optionalcontrol device 1711. An external trigger may act on the control device1711, which in turn activates (turns on) the valve 1709. Once the valve1709 is turned on, the timing fluid 1712 starts advancing within theconduit 1704 and, after a time interval, fills the timing cavity 1703.The pressure of the timing fluid 1704 is applied to the timing diaphragm1701, which acts on the mechanical structure 1702 and destroys it, thusallowing a sample of the external fluid 1708 to fill the isolated cavity1713.

The isolated cavity 1713 may optionally be connected to a samplingchamber 1707 via, without limitation, a tube 1706, channel, or pipe orany other type of fixture or device known in the art that allows fluidiccommunication. The tube 1706 may optionally include a check valve 1705,that allows fluid to flow into the sampling chamber 1707 but prevents itfrom flowing in the opposite direction.

The control device 1711 and the valve 1709 may be electrically active.The control device 1711 may be triggered remotely. The triggering actionin itself may be transmitted to said control device 1711 via, withoutlimitation, a mechanical, acoustical, electrical or electromagneticwired or wireless link. For example, the triggering action may betransmitted to said control device 1711 via a mechanical cable or lever,a serial communication cable, a parallel communication cable, anelectrical triggering cable, an electromagnetic wave using a mobiletelephony network or a radio frequency or satellite connection, apressure wave such as an acoustic or sound wave using an acoustic module(such as sonar and/or a hydrophone, a speaker and a microphone, orsimilar), or any other form of acoustic, electrical, electromagnetic,acoustic or mechanical communication and/or triggers known to the personskilled in the art.

This embodiment allows the sampling device 1700 to acquire a sampleafter a time interval following an external trigger, said time intervalbeing measured, starting from the external trigger, using anelectrically-passive timing mechanism. The sample acquisition operation,including in this case by the piercing and destruction of the saidmechanical structure by the timing diaphragm 1701, is also based onpurely hydraulic and mechanical action, and therefore is electricallypassive.

FIG. 18 shows a sampling device 1800 that includes a sampling chamber1807, in accordance with an embodiment of the invention, that is similarto the above-described device 1700, as shown in FIG. 17, but having amodified conduit 1802 for the timing fluid 1803, and/or a reduced timingcavity volume 1801, thus leading to a decrease of the said timinginterval separating an external trigger from the sampling acquisitionoperation. The timing interval may be further reduced by using a timingfluid 1803 having lower viscosity than timing fluid 1712. Timing fluid1803 may be a gas. The timing interval may thus be reducedsubstantially, in the range of, without limitation, 0.1 ms to 10 ms forcertain applications where rapid response to an external trigger isrequired. In other applications, the time interval may be,illustratively, less than 100 ms, or range from 10 ms to 1 s. In otherapplications, the time interval may range from 1 s to 100 s. In othertime applications the required timing may be significantly longer.

Modifying Sampling Timing by Changing the Timing Cavity Volume

FIG. 19 shows another sampling device configuration, in accordance withan embodiment of the invention. The sampling device 1900, configured toacquire one or several samples from an external fluid 1907, includes atleast two electrically passive sampling mechanisms 1905 and 1906. Thetwo or more sampling mechanisms 1905 and 1906 are designed to acquiretheir respective samples at different times, and differ at least in thefact that the volume of the timing cavity 1902 of one of the samplingmechanisms 1906 is larger than the volume of the timing cavity 1901 ofanother sampling mechanism 1905. The corresponding timing fluid conduits1904 and 1903 may be identical, or they may differ in geometry. The twoor more sampling mechanisms 1905 and 1906 may be within a singlesampling device as shown, or various system embodiments may includemultiple sampling devices having different timing cavity volumes.

Ocean Pollution Monitoring System Deployment

In illustrative embodiment of the invention, a system is provided thatmay be put in place around, without limitation, an industrial facilityas a precautionary measure at an early stage in the project. The systemsmay then be activated remotely for deployment of the sampling arrays,for example, in the event of a serious failure situation, even ifcontrol at the facility has been completely lost. The sampling arraysmay be used, without limitation, to detect the scope of leaks or otherpollution resulting from the failure situation. Additional fail safesmay be implemented which allow for the activation of the devices inseveral modes on remote command from surface via an acoustic or othertype of transmission. Such a system may be deployed as a fully containedunit that sits on the seafloor or other body of water in standby mode,and allows for normal operations at the facility to continue unimpededin absence of any alert or accident.

More particularly, FIG. 20 shows an installation of passive samplingsystems 2001 around, without limitation, oil rigs, offshore platforms orother industrial facility 2004 that may be, for example, located in alarge body of water such as the ocean, in accordance with an embodimentof the invention. The sampling systems 2001 may be located, withoutlimitation, in a fully self contained unit, which may be installed by asurface vessel or ship 2002 that may or may not have the assistance ofan ROV (Remotely Operated Vehicle) 2003. The sampling systems 2001 maybe placed in an accurately known geographical location on the sea floor2010 relative to the wellhead 2011 or as determined by GPS (GlobalPositioning System) coordinates, or both. The sampling system 2001 maybe installed via an installation/retrieval tether 2006 by the surfacevessel. This tether 2006 serves to lower the sampling system 2001 in acontrolled manner from sea level 2005 to the sea floor. The selfcontained unit may have sufficient weight to keep the entire systemnegatively buoyant. In various embodiments, an anchor element 2013 maybe integrated into the self contained element, or otherwise attached tothe self contained unit. The sampling system 2001 may include a buoyancydevice 2012 which serves as a deployment vehicle for a sampling array(described in more detail below) once activated. The system 2001 alsomay include a latch/release mechanism 2014, which allows for thedisengagement of the installation tether 2006 either remotely by thesurface vessel 2002, or physically by the ROV 2003. The latch/releasemechanism 2014 may also act as a latch point for future retrieval. Theinstallation/retrieval tether 2006 may also act as a way to keep thesystem 2001 suspended at neutral weight during installation such thatthe ROV 2003 would be able to move it in the horizontal direction, andaccurately position the sampling system on the sea floor. The finalposition of the sampling system 2001 on the sea floor may be determinedby the ROV sonar with relative position to the wellhead, and riser 2015.In addition, surface sensors located on the surface vessel 2002 such asdownward facing sonar 2016, or similar technology used to locate objectsbelow the ocean surface may be used to determine the final position ofthe sampling system 2001. Additionally emitters, reflectors or otherdevices may be positioned on the sampling system 2001 or installationtether 2006 to aid in the surface detection of the subsea position ofthe system 2001 during the system installation. The ROV 2003 may or maynot be needed for the assistance, guidance or monitoring of the systeminstallation, location and/or detachment of the installation tether2006. The ROV 2003 can be deployed from either the surface facility 2004or the surface vessel 2002 and may be deployed directly from surface orvia an ROV cage tether 2007, ROV cage 2008 and ROV tether 2009.

FIG. 21 shows multiple sampling systems 2001 installed in an array onthe sea floor around an offshore surface facility 2004, in accordancewith an embodiment of the invention. The sampling systems 2001 may bearranged in any manner, layout or number without limitation. Located,without limitation, on the surface facility 2004 may be a surfacetransmitter/receiver 2101 which is able to transmit a control signal2102 through the water column. The signal 2102 may be, withoutlimitation, an acoustic or optical signal, or any other type of signalknown to one of ordinary skill in the art. The transmitted acousticsignal may be projected in all directions and is not limited to onlyvertical or line-of-sight transmission. Each sampling system 2001 mayinclude a subsea receiver/transmitter 2103 which has the ability toreceive the signal 2104. On receipt of the signal 2104 from the surfacefacility 2004, the subsea receiver 2103 may either remain in standbymode, or move to sleep mode, or act as a trigger for further actionwithin the system, depending on the signal received.

In various embodiments, each system 2001 may have the ability totransmit an acknowledgement signal, or small packet of data back to thesurface facility 2004. The sampling systems 2001 may remain in standbymode as long as a transmission command is received to do so from thesurface facility 2004. The system 2001 may be programmed to wake up atpredefined timed intervals and listen for a control signal, such as,without limitation, an acoustic signal or an optical signal, from thesurface facility 2004. If the system 2001 receives the transmission fromthe surface facility 2004, it is an indication of regular operation fromthe surface facility 2004, and the system 2001 can go into sleep modefor a specified period of time in order to conserve power. After thespecified period of time, the system 2001 will again wake up and checkfor the transmission from the surface facility 2004. This may continueindefinitely and keep the systems 2001 in standby mode for the period ofinstallation which may be days, weeks or many months in duration, aslong as normal operations continue. In addition, an extra surfacetransmitter may be installed as a backup system to avoid unintendedactivation and deployment.

FIG. 22 shows an event occurring at the surface facility 2004 and eitherpower is cut to the surface transmitter 2101 (illustratively shown as anacoustic transmitter), or the transmission has been intentionallystopped by someone on the surface facility (i.e. control roompersonnel), in accordance with an embodiment of the invention. In thiscase, there is a loss of transmitted signal 2201 and thus a loss ofreceived acoustic signal 2202 at the subsea acoustic receiver 2103. Theprotocol within the sampling system 2001 may change at this point, andremain awake, continuing to listen for the acoustic transmission fromthe surface facility 2004. At this point the subsea acoustic transmitter2103 may emit a transmission signal or alert 2203 to the surfaceacoustic or optical receiver 2101 as warning to the surface facility2004 that no surface transmission has been received. The samplingsystems 2001 will remain awake in delay activation mode for a period oftime which may be on the order of minutes or hours. If after this periodof time, still no acoustic signal is received from the subsea acoustictransmitter 2103, a release latch mechanism 2204 may be activated by atrigger mechanism for release of the sample array (described in moredetail below).

FIG. 23 shows the result of deployment of a sampling array 2302 byrelease of the release latch mechanism 2204. Each sampling array 2302may include any number of sampling devices 2301 attached to, withoutlimitation, a rope or cable, in any spacing configuration, and mayextend from sea floor to sea level, or any point in between. Uponactivation of the buoyancy device 2012 to disconnect at the releaselatch 2204, the buoyancy device 2012 will ascend through the watercolumn. The buoyancy device 2012 may be attached by a sampling cable toeach of the sampling devices 2301 in series, such that during theascent, each sampling device 2301 is pulled out of the containment unit2303 and into sampling position. Alternatively, each sampling device2301 may itself be buoyant in which case an additional buoyancy device2012 may or may not be used. The vertical spacing of each samplingdevice 2301 may be determined by the length of cable that is installedbetween each sampling device 2301. The entire sampling string may betethered at one end to the containment unit 2303 and anchor element 2013to keep the entire sampling array in position. Each sampling device 2301may be automatically triggered mechanically or electrically as it ispulled from its initial position relative to the containment unit 2303,so as to start the timing fluid for time interval sampling. This triggermay be by Hall Effect sensor, or mechanical switch, or other device withsimilar functionality to allow for activation of the timing fluid. Invarious embodiments, each sampling device 2301 may be triggered bysimply deploying/entering the body of fluid (for example, the body offluid may be used as the timing fluid). Once activated, each samplingdevice 2301 may acquire separate individual samples at specified timedintervals that are preprogrammed prior to installation of the samplingsystems 2001.

The trigger mechanism may control the latching mechanism 2204 byproviding to the latching mechanism 2204 an acoustic signal, an electricsignal, an optical signal, an electromagnetic signal, or a mechanicalsignal, or a combination thereof. As described above, the containmentunit may include a receiver for receiving a control signal that may bean acoustic signal or an optical signal, the trigger mechanismcontrolling the latching mechanism as a function of the control signal.The trigger mechanism may include an acoustic release, a device commonlyused in fields such as oceanography. The latching mechanism 2204 mayinclude a fusible wire and means of sending an electrical currentthrough the fusible wire, leading to the melting of the fusible wire andthe release of the sampling array. The latching mechanism 2204 mayfurther include means to providing mechanical advantage to the strengthof the fusible wire.

FIG. 24 shows deployment of monitoring systems that include near-wellsystems having a closer spacing both vertically 2401 as well ashorizontally 2402. This provides a greater resolution of the pollutionprofile in 3 dimensions at the critical areas near to the wellhead 2011over time to give a more accurate map of the pollution progression. At agreater perimeter from the wellhead 2011, the systems may have a largerspacing horizontally 2404, extend further vertically in the water columnand may have a greater spacing 2403 between each individual samplingdevice 2301 in the sampling array. These sampling arrays may include anynumber of sampling devices in each array depending upon variousparameters such as ocean depth or distance from the wellhead 2011 orboth. The sampling arrays may also be biased or clustered in aparticular direction relative to the wellhead 2011 based on knownvariables such as ocean current direction or ocean depth profile orshore line direction or other such factors.

FIG. 25 shows sampling arrays 2302 deployed in a non-static environment,in accordance with an embodiment of the invention, such as the case whenthere is natural ocean current 2501 or wave motion 2502 due to winds, orother movement within the ocean column. This movement may or may not bein the same direction and may cause one or more sampling arrays 2302 tobe in a position that is not vertically above the original knownanchoring point. In illustrative embodiments, one or multiple devices orsensors may be installed into the sampling array that are capable ofmeasuring the array's actual position. Using such devices, the positionof each sampling device in a sampling array may be accurately determinedover time relative to the known anchor point.

More particularly, a device 2503 may be installed in the sampling arraythat includes a 3-axis accelerometer or tilt meter or inclinometer orcompass or relative bearing device or flow meter or any combination ofsuch devices or similar, such that the position of each sampling device2301 in the string may be accurately determined over time relative tothe known anchor point of the self contained unit. The device 2503 maybe contained in the buoyancy device 2012 at the top of the samplingarray 2302, or at a point near the top of the sampling array 2302.Additionally, any multitude of such devices 2503 may be included atmultiple points along the sampling array 2302 or within the sampledevices 2301. This configuration would allow for the prediction of eachsampling device 2301 position in the case that forces within the oceancolumn are not uniform, such as variable ocean currents, resulting in asampling array 2302 that may or may not be vertically linear.Additionally, the associated sampling devices 2301 and cable of thesampling array 2302 may be designed to be either neutrally buoyant orpositively buoyant as to allow for greater confidence in the predictedposition of each sampling device 2301. The device(s) 2503 would recordtheir continuous positioning data throughout the sample acquisition inorder to provide positional data of each sample device 2301 at eachsample acquisition time for input into prediction models. In addition,this continuous positioning, directionality and or ocean current andflow data may be used in itself for input into prediction models beyondthe point by point positional data provided only at the time of each ofthe acquired samples.

FIG. 26 shows several options for retrieval of the sampling arraysand/or sampling systems after the samples have been acquired, inaccordance with an embodiment of the invention. In various embodiments,a sample array release 2601 may be activated and separated from a latchelement 2602 at the completion of all sampling. The sampling array 2302remains attached to the buoyancy device 2012 which then ascends to sealevel 2005 at the ocean surface. Latch element 2602 may also act as aconnector for future retrieval of the containment unit 2303. At the sametime, the retrieval transmitter 2103 located on or inside the buoyancydevice 2012 may transmit a locator signal 2604, which may be in theradio frequency range for detection and location by the retrieval vessel2002, which may carry a locator device 2605 to detect the location ofthese sampling arrays 2302. In addition, the buoyancy device 2012 may bea color that is highly marine visible for easy visual detection on theocean surface. The retrieval transmitter 2103 may also contain lightsthat will additionally aid in the visual detection and retrieval of thesampling strings, especially during but not limited to night operations.The retrieval vessel 2002 with the locator device 2605 may determine thelocation of the sampling arrays 2302 by radio signal strength or bysignal directionality or by visual observation or any combination ofthese methods. In another case, at the completion of all sampling, asampling array release 2606 is activated which separates the samplingarray 2302 from the latching element 2602 located on the containmentunit 2303, however, the array 2302 is still attached to a retrievaltether 2607. This retrieval tether 2607 allows the sampling array 2302to travel to the ocean surface, but still maintains connection to thecontainment unit 2303 by a connection element 2608. This connectionelement 2608 may be attached to a wire coil that is located within thecontainment unit body that is able to expel cable as the buoyance device2012 ascends to surface. The buoyancy device 2012 may also be of a colorthat is highly marine visible and may contain a retrieval transmitter2103 as described previously. The retrieval tether 2607 may be such thatthe length is enough to allow the buoyancy device 2012 to reach surface,or may be long enough that the tether 2607 itself can extend to surfacefor retrieval of the containment unit 2303 by a mechanical winch system.In this case the buoyancy device 2012 may act as a locator for thesampling array 2302, and also provide a direct connection to thecontainment unit 2303 for subsequent retrieval.

In yet another embodiment, the buoyancy device 2012 may include aseparate retrieval tether 2609 that is attached to the containment unit2303, but is able to spool 2611 itself out as the buoyancy device 2012is released from the containment unit 2303 and ascends through the watercolumn. This tether 2609 may be at a minimum, long enough to reach fromsea floor 2010 to ocean surface 2005. The retrieval tether 2609 may alsobe such that it deploys in multiple stages. One such example would bethat the retrieval tether 2609 is programmed prior to installation torelease from the containment unit 2303 when commanded to do so, andunspool a certain length of cable. This would effectively set the depthof each sampling device relative to the sea floor 2010 for the durationof the timed sampling. Then after a predetermined period of time, or ata given trigger, or at the end of sampling, the retrieval tether 2609unspools until the buoyancy device 2012 reaches the ocean surface 2005.In this case the sampling array 2302 or sampling devices 2301 may or maynot be attached by an attachment line 2610 to the retrieval tether 2609,but the retrieval tether 2909 remains fixed to the containment unit 2303on the sea floor 2010. The attachment line 2610 may be of any length,and may be used as an alternative to the cable/string of sampling array2302 itself. Additionally, the spooling device 2611 may be placed indifferent points within the sampling system 2001, including mounting onor contained within the buoyancy device 2012 itself.

FIGS. 27(a) and 27(b) show the activation of a transmitted acousticsignal that acts as an override for sampling system retrieval, inaccordance with an embodiment of the invention. The surface acoustictransmitter 2101 is capable of transmitting an override acoustic signal2701 to the sampling systems that are in standby mode on the oceanfloor. When an override acoustic signal 2702 is received at the subseaacoustic receiver 2103, the system acts to deploy a buoyancy device 2703that pulls a retrieval tether 2709 fully to the surface. This may beperformed without activation of the sampling array 2302 or samplingdevices 2301. Each unactivated system may be retrieved from the seafloor for subsequent deployment at a later time, or at a differentlocation, or both. In various embodiments, the system may contain asafety protocol, such that activation of the system cannot be triggeredwhile the tether is physically connected to the buoyancy device or otherconnection point. This may be performed by Hall Effect sensor ormechanical safety lock or other method to achieve similar function. Thesystem may be intended for repeated deployment with routine servicingand maintenance. The buoyancy device 2703 may be the same device as thepreviously described buoyancy device 2012, or may be a secondarybuoyancy device. The buoyancy device 2703 may have an additionalfunction whereby the override acoustic signal 2702 is able to selecteither to deploy the sampling array 2302, or to deploy the retrievaltether to the surface, or a combination of either, using a singlebuoyancy device. The buoyancy device 2012 and buoyancy device 2703 maybe combined together in series and deployed independently or may bedeployed simultaneously to provide an easy method for sampling andimmediate retrieval after sampling. The buoyancy device 2703 may also beof a color that is highly marine visible and may contain a retrievaltransmitter 2103 as described previously.

FIG. 28 shows a sampling system that is in standby mode having anadditional buoyancy device 2851 which always remains at ocean surfacelevel 2005. The buoyancy device 2851 includes a surfacetransmitter/receiver device 2854 that also always remains at oceansurface level 2005, and is able to transmit and receive a signal 2853,from a transmitter/receiver 2855 that is located, for example, on thesurface facility 2004 and that is in the radio frequency range. Thisbuoyancy device 2851 is connected by a cable 2850 that may or may not beelectrically connected to the sampling system 2001 and the samplingdeployment buoyancy device 2012. When a trigger signal 2852 is received,as described in previous embodiments, the device 2851 is able to send adeployment command signal via the cable 2850 to release the samplingdeployment buoyancy device 2012. The buoyancy device 2012 and samplingarray 2302 may be physically connected to the cable 2850, or may deployindependently. When deployed, the buoyancy device 2012 may extend fromthe ocean floor 2010 to the ocean surface 2005, or any point in between.In addition, the cable 2850 may also act as a deployment cable for asurface vessel to accurately position the sampling systems on the oceanfloor. The cable 2850 may also act as a retrieval cable such that asurface vessel may retrieve sampling systems 2001 that have not yet beendeployed, or also to retrieve the sampling array 2302 that has beendeployed, or both.

FIG. 29 shows a system that may be deployed for continued monitoring ofan offshore leak progression at a perimeter that may be outside of theinitial deployment around the site, in accordance with an embodiment ofthe invention. The system utilizes deployment of “after accidentdeployment kits” that include one or more sampling systems 2001. Thesekits may be ready in standby on-shore for immediate deployment, and maybe designed for larger perimeter surveys that are customizable invertical sampling spacing 2902 for variable resolution. The deployedsampling systems 2001 may extend from ocean floor to surface, or anyinterval in between. Deployment and retrieval would be done directlyfrom surface using a surface vessel 2002, with location of the samplingsystems 2001 being provided by the surface vessel 2002, as described inprevious embodiments. In addition, the buoyancy device 2012 may belocated at the ocean surface 2005 and may include a GPS system foraccurate location determination. Additionally at any point or amultitude of points within the sampling array 2302 a positioning device2503, as described previously, may be included for accurate predictionof the position of each of the individual sampling arrays or devicesover time. The “after accident deployment kits” may be immediatelyactivated by the surface vessel 2002 as soon as they are placed inposition for monitoring, or they may be installed on a time delaytrigger to start the interval sampling in the future which may beminutes, hours or days.

FIG. 30 shows in detail several possible features of the sampling system2001, in accordance with an embodiment of the invention. Referencenumbers utilized have been described previously. In addition, thesampling system may include any number of sample holder ports 3001 thatmay be used or left empty as desired, and may vary based on parametersin the area where the system will be deployed. Each sampling device 2301may be installed into a sample holder port 3001 and may include anO-ring seal 3002. This seal 3002 may serve to protect the sample inletports 3003 which may be, without limitation, located at the bottom ofthe sampling device 2301. The sampling device 2301 orientation may be inany direction, but a purpose of the O-ring seal 3002 is to protect thesampling inlet ports from contact with the ocean environment while instandby mode. The purpose of the protection includes avoiding anybiofouling or biogrowth occurring at the sample inlet port that mayimpede sampling or contaminate the acquired sample. The O-ring seal 3002may be disengaged as each sampling device is pulled out of thecontainment unit, allowing perfectly clean, unobstructed entry pointsfor the sample fluid to enter the sampling device. The O-ring seal 3002may provide a full pressure seal to hydrostatic pressure, or may beprefilled with fresh water, or any known fluid that rejects biofoulingor biogrowth. This fluid may or may not also be used for hydrauliccompensation at the O-ring seal. The system may be configured such thatthe sample holder ports 3001 automatically fill with seawater at therelease of the buoyancy device 2012, such as by opening a fluid inlet atthe release of the buoyancy device.

According to related embodiments of the invention, a sampling system mayinclude location devices such as global positioning systems (GPS units).Said sampling system may be equipped with emitters capable to send theGPS coordinates either via a satellite data link, or via the phonenetwork system or by other means of radio communication. Once it hasbeen released from the ocean floor and has reached the ocean surface, asampling system may emit radio waves, electromagnetic, acoustic oroptical beacon signals, so as to alert ships or other ocean vehicles ofits presence and to send current position to a data collection system.The GPS units and communication emitters may be built into, or attachedto each sampling unit on the sampling system, and/or to a buoyancydevice.

Monitoring System (Time Stamping and Sample Acquisition Monitoring)

FIG. 31 shows a monitoring system for recording sample acquisition timeof each sample. More particularly, sample device 3102 includes apressure active device 3104, in accordance with an embodiment of theinvention. The sample device may be, without limitation, as described inabove embodiments, configured to acquire a sample from an external fluid3101. The sampling device 3102 includes a sample chamber 3103 forcollecting the sample. Said sample chamber 3103 may incorporate in itsinterior a pressure-active device 3104 that responds to pressure withinthe sample chamber 3103. The pressure-active device 3104 may be incommunication with a processor 3106 for analyzing and/or recording thesignal from said pressure-active device 3104. The processor 3106 mayinclude an amount of electronic memory in the form of random accessmemory, flash memory, permanent memory, electrically erasableprogrammable memory or any other form of electronic memory known in theart. The pressure-active device 3104 may be a pressure sensor, apressure switch, a pressure gauge, a pressure transducer, or any otherdevice known in the art that can transform a pressure variation into asignal.

The processor 3106 may be in communication with a second pressure-activedevice 3105 that is placed in and responds to the pressure of theexternal fluid 3101. The processor 3106 may further be in communicationwith a remote system 3107, to which it may transmit data via a wired orwireless link 3110.

If the pressure-active device 3104 is a pressure sensor, the processor3106 may record a pressure curve 3108 of the pressure inside thesampling chamber 3103, and by analyzing the data from said pressurecurve it may calculate the exact moment timestamp (t_(samp)) of thesample acquisition initiation. The timestamp of the sample acquisitiont_(samp) can be inferred, for example, by monitoring the sample chamberpressure sensor for a significant deviation from the initial pressure inthe sample chamber (p_(ini)).

In various embodiments, the processor 3106 may process the pressure dataoriginating from pressure sensor 3104 so as to determine a samplefill-up duration Δt by recording the time (t_(fill)) when pressurestabilizes within the sample chamber 3103, and subtracting from thisvalue the time corresponding to beginning of the sample acquisitiontsamp: Δt=t_(fill)−t_(samp)

In various embodiments, the processor 3106 may process the pressure dataoriginating from pressure sensor 3104 to determine the total volume(V_(samp)) of the sample acquired. This volume can be inferred byknowing the volume V₀ of the sample chamber 3103 and the value p_(ini)of the initial pressure in the sample chamber 3103 prior to sampleacquisition, the value p_(fin) at which pressure has stabilized in thesample chamber after the sample acquisition, and the pressure p_(ext)measured by the pressure sensor 3105 monitoring the pressure of theexternal medium 3109.

The processor 3106 may determine V_(samp) by using the followingformula, which assumes the sample acquisition process as beingisothermal and the gas initially contained in the sample chamber to bean ideal gas, in which case V_(samp)=V₀(1−p_(ini)/p_(fin)).

A difference between p_(fin) and p_(ext) may be interpreted by processor3106 as evidence of clogging during the sample acquisition process.

If the pressure-active device 3104 is a pressure switch, the moment ofthe activation of the pressure switch as recorded by the processor 3106corresponds to the timestamp of the sample, t_(samp).

Integration of Optical Elements within or Around the Sample Chamber

According to an embodiment of the present invention, a sample chamber ofone of the above-described sampling devices may include optical elementsfor performing a measurement of, without limitation, turbidity,absorbance, color, transmittance, autofluorescence, or fluorescence, orany combination thereof.

The sample chamber may incorporate certain optical components, eitherinside the sample container or in its proximity, in order to assure thatthe light travels across or around, or otherwise interacts with thesample in an optimal way.

Said sample chamber may be equipped, without limitation, with: one orseveral optical windows allowing an optical measurement to be performedon the sample contained within the sample chamber, one or multiple lightsources, optical detectors, sensors or recording devices (with nolimitation: cameras, individual photodiodes or arrays thereof, othertypes of optical sensors, phototransistors, avalanche photodiodes,photomultipliers), mechanical positioning assemblies, fibers,diaphragms, mirrors, optically absorbing surfaces, optical filters orany other type of optical component or device known to the personskilled in the art, or any combination or configuration thereof.

Data obtained from the optical elements equipping the sample chamber maybe used to measure the exact time of the sample acquisition (itstimestamp). As an example, a processor could monitor a change in theoptical properties of the sample chamber. Said processor may processdata from an absorbance measurement performed on the acquired sample ata wavelength where the sample fluid absorbs light (such that themeasured absorbance will be higher after sample acquisition than priorto it). Alternatively, said processor may use the presence of an opticalsignal (or the lack thereof) to infer a deviation of the light path dueto a change in optical refraction index that is indicative of a samplebeing present within the sample chamber.

Any other type of measurement, optical or not, that is known to theperson skilled in the art, may be used to determine whether a sample hasbeen acquired within the sample chamber. This may include a conductivitymeasurement, a temperature measurement, an electrochemical measurement,an optical measurement, a physical measurement, a force measurement, adeflection measurement, a chemical measurement, a biological orbiochemical measurement, or any combination thereof.

Passive Timing Mechanism of Improved Precision

As described above in the background section, assume one sample needs tobe acquired every hour for a period of twenty four hours. Twenty foursampling devices are deployed at t=0, device numbered n (1<n<24) havinga time constant of n hours prior to triggering the acquisition of itscorresponding sample. If there is a ten percent error in the fluidicclock of each sampling device, that means that it is likely that theorder of the sampling events will be disturbed. For example, the 10thdevice may acquire its sample at t=11 h, and the 11th device at t=10 h,thus they will be out of order.

A system is provided that advantageously includes a number n of samplingdevices that are being timed by fluidic clocks in such a manner that thetiming mechanism of the n+1st device is triggered by the acquisition ofthe nth sample, in accordance with an embodiment of the invention.Illustratively, in the above-described application, each device couldhave a time constant of 1 hr (or 60 minutes). A ten percent random errorin the timing means that the time interval between one sample n and thesubsequent one n+1 will carry an absolute error of 6 minutes, but allthe samples will be acquired in sequence.

More particularly, FIGS. 32-34 show embodiments of the invention thatresult in passive timing mechanisms of improved precision. A samplingdevice is provided that includes multiple sampling mechanisms capable oftiming and performing the acquisition of multiple (n) samples in anelectrically-passive way, where the electrically-passive timingmechanism corresponding to sample i+1 is triggered at a time instantthat is related to the time of acquisition of sample i. The samplingdevice acquires samples from an external fluid.

As shown in FIG. 32, an exemplary sampling device 3200 may include twotiming diaphragms 3207 and 3208, two connected timing cavities 3205 and3206, two mechanical structures 3203 and 3204 and two isolated cavities3213 and 3214. The first mechanical structure 3203 separates theexternal fluid 3201 from the first isolated cavity 3213.

The sampling device 3200 further includes a conduit 3210 that may be amicrofluidic channel or a capillary tube, and that may have a predefinedgeometry. Upon applying pressure to a timing fluid 3202 within theconduit, said timing fluid 3202 being a liquid or a gas, said timingfluid 3202 advances within the conduit 3210 at a speed, for example,that may be dictated by the applied pressure, the predefined channelgeometry and known timing fluid properties. The timing fluid conduit3210 is also connected, by a tube or similar fluidic connection 3209, tothe second mechanical structure 3204. Upon reaching the connected timingcavities 3205 and 3206 and filling them after a timing interval, thetiming fluid 3202 applies pressure to the two timing diaphragms 3207 and3208 simultaneously, thus destroying their corresponding mechanicalstructures 3203 and 3204, for example, by piercing and consequentlyrupturing and/or collapsing them.

The first mechanical structure 3203, once destroyed, allows a sample ofthe external fluid 3201 to be acquired by enabling the external fluid toenter the isolated cavity 3213, which may then further lead to asampling chamber via a channel, tube pipe or any other type of fluidicconnection 3211. The second mechanical structure 3204, once destroyed,opens a passage for the timing fluid 3202 to enter the timing fluidconduit 3212 of a subsequent sampling mechanism, thus acting as aneffective trigger for timing the acquisition of the next sample.

FIG. 33 shows two sampling devices 3301 and 3302, each as described byFIG. 32, such that the timing fluid conduit 3212 of sampling device 3303is connected to the second mechanical structure 3204 of sampling device3301. The tubes 3303 and 3209 that allow the fluidic communicationbetween the timing fluid and the second mechanical structures 3204 and3304 of sampling devices 3301 and 3302 may be distinct.

In the configuration shown in FIG. 33, the acquisition of a sample bydevice 3301 happens simultaneously with the destruction of themechanical structure 3204, which allows the timing fluid to enter device3302 and, following another timing interval, the device 3302 willacquire its own sample. Any number of such sampling devices may beconnected in sequence, each sampling device acquiring its sample afterbeing triggered by the previous sampling device.

FIG. 34 shows a related embodiment of FIG. 33, showing the same twosampling devices 3301 and 3302, and further showing the tubes 3303 and3209 allowing the communication of the timing fluid with the secondmechanical structures 3204 and 3304 of the sampling devices 3301 and3302. It is further shown that the tubes 3303 and 3209 may be connectedusing a common manifold 3403 or a similar fluidic connection.

It is understood that such operation can be implemented using otherembodiments of the sampling mechanism. For example, using pistonsinstead of timing diaphragms, as described previously, to pierce themechanical structures.

Microbiological Measurement

It may be advantageous to allow a sample to incubate for a certainperiod of time, so as to allow a certain type of microorganism tomultiply and grow. According to further embodiments of the presentinvention, a sampling system may be equipped with a sample chamber thatis partially pre-filled with a culture medium. Said culture medium maybe selective, allowing only select classes of microorganisms to developand grow. Said sample chamber may be configured so that, upon sampleacquisition, the sample comes in contact with the culture medium. Theculture medium is selected such that, if the sample is contaminated witha select class of microorganisms, these will multiply, over a period oftime called the incubation period. For example, and without anylimitation, certain commercial culture media and bioreagents exist (suchas, without limitation, the bio-reagents commercialized under the brandnames ReadyCult and Colilert), that allow coliform bacteria to incubate,and over a period of incubation time of several hours the samples changecolor or fluorescence properties which can lead to the detection andquantification of the said coliform bacteria or of certain classesthereof.

Said sample chamber may include a temperature control mechanism thatensures that the sample temperature is maintained within a range that isoptimal for sample incubation.

Said sample chamber may include chemical and/or biological reagents,and/or biocides that react in the presence and/or of the quantity ofsaid microorganisms. Detection of said reaction result may be performedoptically, for example (without implying any limitation) by performingan optical absorption measurement, a color measurement, or by monitoringits fluorescence, or its auto-fluorescence.

This embodiment may be combined with other embodiments of the presentinvention.

Built-In Redundancy

Due to the impracticality of on-line operation monitoring for passivedevices such as the above-described devices and systems, it may beadvantageous to incorporate various redundancy schemes, to minimize thechance of failure due to unforeseen circumstances. Redundant timing andsensing mechanisms, rendered possible by the extreme miniaturization maybe integrated within the device. All critical device components may bebuilt in multiple copies on a single chip, providing parallel fluid andmeasurement paths in case of failure (e.g., due to channel clogging orsensor malfunction). Single chips may be designed to include multiplesensor chambers for sample analysis, as well as multipleacoustic-emission isolation diaphragms and associated cavities, thusproviding multiple assays and hence improved measurement statistics oncethe devices are recovered at the surface. Multiple timing mechanismshaving different time constants may be incorporated onto a single deviceas well, thus providing a measurement time-series to monitor theevolution of a parameter of interest over a device well injection andretrieval cycle. The resulting device architecture can be extremelyrobust and should be capable of providing a reliable measurement even inthe most adverse environmental conditions.

Harsh Environment Compatibility

Completely passive systems represent an advantageous approach to sensingin the very harsh environments specific to the oilfield (e.g., hightemperature and pressure (HPHT), corrosive fluids, severely constrainedgeometry). The above-described embodiments allow the deployment of smartpassive devices that are capable of performing a number of specific,well-defined functions in, without limitation, the subterraneanenvironment surrounding an oil well, without requiring power,monitoring, or telemetry. Such smart passive devices can be deployeddownhole by pumping along with frac- or other injected fluids, or theycan be integrated within existing oilfield measurement tools such as theMDT tool, the FMT tool or the SFT tool. The smart devices may acquire,react with, and isolate a sample of downhole fluid, and, once retrievedfrom the reservoir, they can be interrogated by optical, electrical orother means to provide information about the environment they have beenexposed to (e.g. chemical or physical properties of the fluidsencountered) as well as about the times when the measurements wereperformed. Additionally, as described above, the device can emit burstsof acoustic signals at pre-defined times which can allow devicelocalization by, without limitation, triangulation using multiplemicrophones.

All the device functionalities recited above may be implemented inmultiple applications, and are not limited in any way to oilfieldmeasurements. Examples of different applications include, but are in noway limited to: submarine deployment of such systems as in a body ofwater, river, lake, sea, ocean; measurements within water wells andaquifers; waste water storage tanks and reservoirs, and the monitoringthereof; and injection wells for carbone dioxide sequestration.

The above-described embodiments are not constrained to a specificsensing technology—several technologies are compatible with and can beintegrated within such a smart passive device, such as, withoutlimitation: purely chemical sensors (e.g. titration reactions),corrosion sensors, MEMS sensors, electrochemical sensors, andfunctionalized nanoparticles. The purely passive devices may bemission-specific so as to integrate only those functions that areabsolutely paramount to performing and later interpreting the specificmeasurement (or chemical reaction) of interest; all additionalfunctionality will be provided externally after recovery. This purelypassive approach therefore minimizes the risk of system failure due toenvironmental issues.

Ultimate Size Miniaturization

Besides the capability to survive a harsh environment, a fully passivesystem provides ultimate miniaturization capabilities. Typically,physical transducers occupy only a very small percentage of the totalpackage size in miniaturized sensors (such as those using MEMStechnology), the rest being occupied by electronics and connections. Apassive approach eliminates the need to operate electronics down-hole,and thus can lead to impressive size reduction. The use of small,passive devices, that may be fabricated using, without limitation, MEMStechnology, permits deployment within pores and/or fractures of therock. Such deployment may be performed, for example, as part of aproppant formulation during hydraulic fracturing operations.

Manufacturing Techniques

The above-described devices may be employed in harsh environments andrequire resistance to high external mechanical stresses. Furthermore, invarious implementations, a large-volume manufacturing technology thatallows cost-effective miniaturization of the complex device geometriesis often desirable. Pure microelectromechanical (MEMS) technology,allowing extreme miniaturization with ultimate dimensional control, maybe an excellent choice for laboratory scale experiments and fieldtesting, but may be less ideal for real, large-scale field deployment:it is expensive; MEMS materials are extremely brittle leading to limiteddevice survivability; and the fabrication technology, based on planarlithographic mask-based processes, often imposes important devicegeometry constraints. Fabrication using a hybrid MEMS-AMM (additivemicro-manufacturing) approach may preserve the advantages but overcomethe limitations of pure MEMS technology, allowing the industrializationand large-scale production of the devices at a competitive cost.

In the embodiment shown in FIG. 35, the structural part/elements of thedevice body 3501 and the mechanical structure 3506, which separate theisolated cavity 3507 from the exterior environment 3508, may be built asa monolithic part. Illustratively, both the mechanical structure 3506and the structural elements 3501, which are coupled to and support themechanical structure 3506, may be fabricated using a manufacturingtechnology such as, for example and without limitation: MEMSfabrication, additive manufacturing (e.g., stereolithography, polyjet,inkjet printing, plastic laser sintering, direct metal laser sintering,fused deposition modeling, 3D printing in ceramic technology, etc.),micro injection molding, ceramic forming, high-speed micromachining, andelectrical discharge machining. The material for manufacturing themechanical structure 3506 and the device body 3501 is preferable of abrittle nature, allowing rapid collapse, rupture or fracturing once itsmechanical integrity is compromised. Such rapid collapse would allow thedevice to emit a strong acoustic signal. Materials that could besuitable for manufacturing the mechanical structure and the device bodyinclude, without limitation: glass, silicon, ceramic and/or sapphire.The monolithic nature of the mechanical structure and structuralelements may cause both to collapse simultaneously, further enhancingthe acoustic emission.

The device also includes a passive timing mechanism 3504, which allows atiming cavity 3505 to fill with fluid over time, the pressure of saidfluid eventually acting on the timing diaphragm 3503 so as to push thepiercing structure 3502 into the mechanical structure 3506, causing itscollapse. The passive timing mechanism 3504 may be a porous structureallowing slow seepage of fluid from the external environment 3508 intothe timing cavity 3505, or it may be a fluidic circuit integrating afluidic conduit that limits the rate at which the timing cavity fillswith fluid. The timing mechanism 3504 may be bonded to the timingdiaphragm 3503, the structural part/elements 3501 of the device body, orboth, using, for example, an adhesive, ultrasonic welding, e-beamwelding, soldering, or combination thereof.

The timing diaphragm 3503 may be manufactured out of any materialallowing sufficient flexibility, preferably as a thin layer. This couldbe a metal layer that is bonded to the structural elements 3501 of thedevice body using, for example and implying no limitation, an adhesive,ultrasonic welding, e-beam welding, soldering, or combination thereof.The timing diaphragm 3503 may be an elastomeric membrane, or a plasticfilm, that is adhesively attached to the structural elements/part 3501.In various embodiments, a double-sided adhesive tape may be utilized. Asshown in FIG. 35, the structural element(s) 3501, which are coupled toand support the mechanical structure 3506, along with the timingdiaphragm 3503 (and in some embodiments other portions of the passivetiming mechanism 3504) combine to form the isolated cavity 3507.

The piercing structure 3502 may be manufactured separately, using,without limitation, MEMS, ceramic or 3D-printing technology. Since thepiercing structure 3502 is meant to apply local force to the mechanicalstructure 3506 in order to pierce it, rupture it or collapse it, itneeds to be manufactured out of hard material capable to withstandsignificant compressive stress. Preferred materials would be silicon,ceramic, metal or hard plastics.

FIG. 36 shows another embodiment of the device, where the structuralelements of the device body 3601, and the mechanical structure 3602, aremanufactured separately and then bonded using an appropriate bondingmethod, such as one of the technologies described above. The structuraldevice body elements 3601 may be manufactured using traditionalmachining, or additive manufacturing (e.g., stereolithography, polyjet,inkjet printing, plastic laser sintering, direct metal laser sintering,fused deposition modeling, 3D printing in ceramic technology, etc.).Ideally, the materials used for the structural device body elements 3601are selected to be able to withstand the stresses that are to beencountered during field deployment, e.g. injection in a well duringhydraulic fracking operations. Such stresses can be either dynamic orstatic. Dynamic stresses are generated when devices pass through thepumps, or when they are flowing along with proppant before reaching thefractures. Static stresses are of isotropic (hydrostatic) nature (due,for example, to the pressure of the surrounding environment), or ofnon-isotropic nature (due, for example, to the fracture closure force).Some ductility may advantageously help in withstanding dynamic stresseswithout collapsing. Preferred materials for the structural body elements3601 include metals, strong plastics, and resins. Other materials mayinclude ceramics, glass or silicon, which can be sufficiently strong butare more brittle.

The mechanical structure 3602, on the other hand, may be manufactured ina strong brittle material that will rapidly rupture or collapse when thepiercing structure 3502 starts applying stress. Such rapid collapse isimportant for the device to emit a strong acoustic signal. Materialsthat could be suitable for manufacturing the mechanical structure 3602include, without limitation: glass, sapphire, silicon and ceramic.Illustratively, MEMS technology, using silicon or glass substrates iswell adapted to manufacturing the mechanical structure 3602. MEMSetching techniques that may be used include deep reactive ion etching,inductively coupled plasma reactive ion etching, isotropic wet etching,and anisotropic wet etching.

Compared to the device shown in FIG. 35, the device of FIG. 36 maytherefore better withstand real-world applications, and particularlyresist external mechanical stresses. This is due to the choice of theappropriate materials and manufacturing techniques for each part of thedevice, according to its function.

Furthermore, in FIG. 37, the structural elements/part of the device bodyof FIG. 36 is shown incorporating additional protection features 3701and 3702, such as, without limitation, various types of lap joints, forthe mechanical structure and for the timing mechanism, respectively.This may provide yet better resistance to mechanical stresses, byisolating and cushioning the brittle elements of the device. Suchprotective features could be incorporated in all the designs presented,and will not be systematically described.

FIG. 38 shows another embodiment of the invention, in which the devicebody structural elements/parts 3801 and the timing diaphragm 3802 aremanufactured as a monolithic structure, and bonded to the other deviceelements such as the mechanical structure 3602, and the timing mechanism3504. Different methods can be applied for manufacturing the monolithicstructure mentioned above, but additive manufacturing has importantpotential advantages such as the ability to create intricate geometriesat small scale. Possible additive technologies that may be appliedinclude: stereolithography, polyjet, inkjet printing, plastic lasersintering, direct metal laser sintering, fused deposition modeling, 3Dprinting in ceramic technology, and other similar technologies known inthe art that are commercialized under different names.

Similarly to FIG. 37, FIG. 39 shows the structural elements/part of thedevice body of FIG. 38 incorporating additional protection features 3901and 3902 for the mechanical structure and timing mechanism,respectively, in accordance with various embodiments of the invention.The additional protection features 3901 and 3902 may include, withoutlimitation, various types of lap joints. This may provide yet betterresistance to mechanical stresses, by isolating and cushioning thebrittle elements of the device. Such protective features could beincorporated in all the designs presented, and will not besystematically described.

FIG. 40 shows a device in which the structural elements/body parts 4001,timing diaphragm 4002, and piercing structure 4003 are manufacturedmonolithically, in accordance with an embodiment of the invention.Different methods can be applied for manufacturing the monolithicstructure mentioned above, but additive manufacturing has importantpotential advantages such as the ability to create intricate geometriesat small scale. Possible additive technologies that may be appliedinclude: stereolithography, polyjet, inkjet printing, plastic lasersintering, direct metal laser sintering, fused deposition modeling, 3Dprinting in ceramic technology, and other similar technologies that arecommercialized under different trade names. Such devices may also bemanufactured using precision plastic injection molding.

Similarly to FIGS. 37 and 39, FIG. 41 shows the structural part of thedevice body of FIG. 40 also incorporating additional protection features4101 and 4102 for the mechanical structure and timing mechanism,respectively. The additional protection features 4101 and 4102 mayinclude, without limitation, various types of lap joints. This mayprovide yet better resistance to mechanical stresses, by isolating andcushioning the brittle elements of the device. Such protective featurescould be incorporated in all the designs presented, and will not besystematically described.

FIG. 42A shows a lateral cross-section of a device where the structuraldevice body parts and the piercing structure 4201 are manufacturedmonolithically, including hinges/linkages 4202 that allow attaching andcentering the piercing structure 4201 within the device, while providingthe piercing structure 4201 the ability to move in a directionperpendicular to the plane of the linkages, in accordance with anembodiment of the invention. FIGS. 42B and 42C show top views of thedevice presented in FIG. 42A, exemplifying possible hinge geometries.

The structural device body parts may be bonded to the timing diaphragmusing different techniques listed above. Different methods can beapplied for manufacturing the monolithic structure mentioned above, butadditive manufacturing has important potential advantages such as theability to create intricate geometries at small scale. Possible additivetechnologies that may be applied: stereolithography, polyjet, inkjetprinting, plastic laser sintering, direct metal laser sintering, fuseddeposition modeling, 3D printing in ceramic technology and other similartechnologies that are commercialized under different trade names.

FIG. 43 shows a device where the structural elements/body parts 4301 andtiming diaphragm are built monolithically, but integrating also thetiming cavity 4302, in accordance with an embodiment of the invention.FIG. 44 shows a similar device, where the monolithic part of the devicefurther incorporates the piercing structure 4403. Different methods canbe applied for manufacturing the monolithic structures mentioned aboveand shown in FIGS. 43 and 44, but additive manufacturing has importantpotential advantages such as the ability to create intricate geometriesat a small scale, and in strong materials. Possible additivetechnologies that could be applied include: stereolithography, polyjet,inkjet printing, plastic laser sintering, direct metal laser sintering,fused deposition modeling, 3D printing in ceramic technology and othersimilar technologies that are commercialized under different tradenames. Such devices may also be manufactured using precision plasticinjection molding.

In general, the above-described devices may be monolithic or hybriddevices. In various embodiments, the structural elements, the mechanicalstructure, the timing mechanism and/or the piercing structure may bemanufactured using additive manufacturing technologies selected from thegroup consisting of stereolithography, polyjet, inkjet printing, plasticlaser sintering, direct metal laser sintering, fused depositionmodeling, 3D printing in ceramic technology, and combinations thereof.In various embodiments, the structural elements, mechanical structure,timing mechanism, and/or piercing structure are manufactured using MEMSetching techniques selected from the group consisting of deep reactiveion etching, inductively coupled plasma reactive ion etching, isotropicwet etching, anisotropic wet etching and combinations thereof.

FIG. 45 shows a device where the mechanical structure 4501 furtherincludes an etched geometry 4502 on the top surface, near the center, inaccordance with an embodiment of the invention. Such etched geometry mayhelp amplify stresses when the piercing structure starts applying force.Ideally, such etched geometry may be placed, without limitation, inregions of the mechanical structure that are normally under compressivestress, but that develop tensile stress under the action of the piercingstructure. In the case of geometry etched on the top side of themechanical structure, this may correspond to its center area, close towhere the piercing structure applies its force. Regions other than thecenter area of the top surface of the mechanical structure 4501 may alsobe etched.

FIG. 46 shows a device where the mechanical structure 4601 furtherincludes an etched geometry 4602 on the bottom surface, near the outeredge, in accordance with an embodiment of the invention. Ideally suchetched geometry should be placed in regions of the mechanical structurethat are normally under compressive stress, but that develop tensilestress under the action of the piercing structure. In the case ofgeometry etched on the bottom surface of the mechanical structure, thismay correspond to its outer edge. Regions other than the outer edge ofthe bottom surface of the mechanical structure 4501 may also be etched.

FIG. 47A shows typical elastic deflection of a circular clamped membraneunder hydrostatic pressure applied to the top side, in accordance withan embodiment of the invention. The deflection and radius are normalizedon the graph. The region of compressive stress at the top membranesurface is contained within the inflection radius (which corresponds toa circular region of diameter D/√3, D being the membrane outerdiameter).

FIG. 47-B shows a cross-section through a circular mechanical structure4702, and one possible positioning of the top-side etched geometry 4703,contained between the inflection radius of the circular structure 4702,in accordance with an embodiment of the invention.

FIGS. 47C, 47D, 47E shows top views of possible top-side etchedgeometries: radial etch configuration (FIG. 47C), concentric circlesetch configuration (FIG. 47E) and combined radial and concentric circlesconfiguration (FIG. 47D), in accordance with various embodiments of theinvention.

FIG. 48A shows a mechanical structure 4801 geometry which has amembrane-like portion delimited by etching 4802, in accordance with anembodiment of the invention. The membrane-like portion of the mechanicalstructure may have further geometries 4803 etched into it, on eitherside, as shown in FIGS. 48B and 48C.

It is understood that partial etched geometries of the mechanicalstructure, or of other device parts, could be incorporated in all thedesigns presented, and will not be systematically described.

FIG. 49 show different ways to manufacture the passive timing mechanismof the device, in accordance with various embodiments of the invention.More particularly, FIG. 49A shows the passive timing mechanism 4901 as aporous structure allowing slow seepage of fluid from the externalenvironment into the timing cavity. The timing cavity 4902 may beintegrated to the passive timing mechanism, as shown in FIG. 49B, or maynot be integrated, as shown in FIG. 49A. FIGS. 49C and 49D show thepassive timing mechanism as a fluidic circuit 4903 integrating a fluidicconduit 4904 that limits the rate at which the timing cavity fills withfluid. The timing cavity 4905 may or may not be integrated to thepassive timing mechanism.

FIG. 50 shows the device of FIG. 35, but where the timing diaphragm isreplaced by a piston structure 5001, which uses a moving seal 5002 toallow movement without allowing fluid to flow past. It is implied thatthe configurations described above using a timing diaphragm can beadapted to using a piston in a straight-forward manner.

In summary, the above-described devices enable a variety offunctionalities. These functionalities include, without limitation, thefollowing:

1. mechanical protection and hermetic transport of the device within theexternal environment (by pumping or injection), or deployment withinvarious measurement tools;

2. sample acquisition, material release and/or chemical reaction in-situat pre-defined times, using passive microfluidic timing mechanisms thatmay include, without limitation, a diaphragm or a piston;

3. sample isolation from external medium prior to and after acquisition(cross-contamination control);

4. integrated redundancy mechanisms to assure correct device operationeven in cases of failure of one of the sample mechanisms;

5. monolythic integration with standard sensor technologies;

6. three-dimensional positioning using coded and/or uncoded acousticsignal emission;

7. external sensor interrogation capability after retrieval at thesurface;

8. filtering

9. measuring viscosity of an external fluid;

10. maintaining a sample at high pressure after sample acquisition, toensure sample integrity and single-phase character;

11. complex sample manipulations, filter backflushing, and transferbetween vials;

12. use of a manifold in sampling system

13. chemical/biochemical/microbiological sample measurement(s);

14. integration of optical elements within or around the sample chamber

15. daisy chain configuration of multiple sampling systems;

16. external control of sampling time/triggered sampling implementation;

17. modifying sampling timing using different passive timing durations(for example, by changing the timing cavity volume);

18. pollution monitoring system/deployment

19. monitoring functionality (for example, time stamping and/or sampleacquisition monitoring)

The above-described devices provide robust, highly miniaturized smartpassive sample chambers/vessels that can be integrated with severalsensor technologies to perform critical in-situ measurements for,without limitation, the oilfield, the ocean, or a living body, or toprovide information about the positioning of devices during fluidinjection or fracturing operations. One of the main features of thedevice is its capability to provide a robust timing mechanism toperform, for example, measurements or material release on a pre-defined(or post-inferred) schedule, and/or to emit acoustic signal sequences,which will allow triangulation of the vessel position, thus indicatingfluid movement and fracture propagation, within a hydrocarbon reservoir,or other pressurized formation or system. From fracture propagationmodeling relative to induced pressures, formation mechanical propertiesand stress analysis can be performed in-situ. The device may beintegrated with standard sensing technologies, allowing a specificmeasurement or set of measurements to be performed on an isolated fluidsample. The device may also be utilized as part of a proppantformulation during hydraulic fracturing jobs, whereas the passivedevices are mixed with slurries and sand grains and are injectedalongside into a formation. The device may be used to as a vehicle fortime-release of particles, chemical products, or pharmaceuticalproducts. The device may be used in autonomous devices, for example, onrobots such as marine remotely-operated underwater vehicles, autonomousunderwater vehicles, airborne or ground drones and vehicles, and othertypes of robotic equipment. The device may be used to monitor flow ofexternal fluids/gases/pollution/contamination in and around, withoutlimitation, cities, chemical plants, nuclear sites, remote regionswithout power, offshore platforms and other oilfield structures,military missions and battlegrounds.

These combined capabilities result, without limitation, in a veryversatile device capable of being implemented within a tool or injectedor otherwise deployed in a formation, or living body, or other body offluid, to provide measurements on samples acquired and/or to releaseparticles, at different locations in, without limitation, an oilreservoir, living body, or other body of fluid, and at multiple times,and to communicate its position via, for example, acoustic emission.

The embodiments of the invention described above are intended to bemerely exemplary; numerous variations and modifications will be apparentto those skilled in the art. All such variations and modifications areintended to be within the scope of the present invention. These andother obvious modifications are intended to be covered by the claimsthat follow.

What is claimed is:
 1. A device comprising: an isolated cavity that isinitially inaccessible to an external fluid; a device body including oneor more structural elements supporting a mechanical structure, themechanical structure separating the isolated cavity from the externalfluid; a piercing structure for piercing the mechanical structure; and amembrane, wherein pressure applied to the membrane drives the piercingstructure into the mechanical structure, causing the mechanicalstructure to collapse, rupture and/or fracture, opening a passage forthe external fluid to enter the isolated cavity.
 2. The device accordingto claim 1, wherein the isolated cavity is in fluidic communication witha sampling chamber.
 3. The device according to claim 2, furthercomprising a tube coupled to the isolated cavity, the tube furthercoupled to a sampling chamber such that external fluid from the isolatedcavity can flow into the sampling chamber.
 4. The device according toclaim 1, further including a one-way check valve between the isolatedcavity and the sampling chamber that allows fluid flow into the samplingchamber.
 5. The device according to claim 1, further comprising anelectrically passive timing mechanism including a fluidic timing cavity,wherein at the end of a timing interval fluid within the timing cavitydrives the piercing structure into the mechanical structure, causing themechanical structure to collapse, rupture and/or fracture.
 6. The deviceaccording to claim 5, wherein the electrically passive timing mechanismincludes a fluidic circuit that allows the external fluid to enter thefluidic timing cavity.
 7. The device according to claim 1, wherein thestructural elements are made of a material that is different from themechanical structure.
 8. The device according to claim 1, wherein thestructural elements include a material selected from the groupconsisting of a ceramic, metal, a plastic and a resin, and combinationsthereof, and wherein the mechanical structure includes a materialselected from the group consisting of silicon, ceramic, sapphire andglass, and combinations thereof.
 9. A method of making the device ofclaim 1, the method comprising using a 3-d printing technique to makethe isolated cavity, the device body, the membrane and/or the piercingstructure.
 10. The method according to claim 9, wherein the 3-d printingtechnique is selected from the group consisting of stereolithography,polyjet, inkjet printing, plastic laser sintering, direct metal lasersintering, fused deposition modeling, and combinations thereof.
 11. Amethod for acquiring a sample from a fluid, the method comprising:deploying a device in the fluid; the device including: an isolatedcavity that is initially inaccessible to the fluid; a device bodyincluding one or more structural elements supporting a mechanicalstructure, the mechanical structure separating the isolated cavity fromthe external fluid; a piercing structure for piercing the mechanicalstructure; and a membrane; and applying pressure to the membrane so asto drive the piercing structure into the mechanical structure, causingthe mechanical structure to collapse, rupture and/or fracture, opening apassage for the external fluid to enter the isolated cavity.
 12. Themethod according to claim 11, wherein the device further includes anelectrically passive timing mechanism including a fluidic timing cavity,the method further including: driving, by the fluid within the timingcavity, the piercing structure into the mechanical structure, causingthe mechanical structure to collapse, rupture and/or fracture.
 13. Themethod according to claim 12, wherein the electrically passive timingmechanism includes a fluidic circuit that allows the fluid to enter thefluidic timing cavity.
 14. The method according to claim 11, wherein thedevice further includes a sampling chamber in fluidic communication withthe isolated chamber, the method further comprising acquiring a sample,in the sample chamber, of the fluid that entered the isolated cavity.15. The method according to claim 14, wherein the device furtherincludes a tube coupled to the isolated cavity, the tube further coupledto a sampling chamber such that fluid from the isolated cavity can flowinto the sampling chamber.
 16. The method according to claim 14, whereinthe device further including a one-way check valve between the isolatedcavity and the sampling chamber that allows fluid flow into the samplingchamber.
 17. The method according to claim 11, wherein the structuralelements are made of a material that is different from the mechanicalstructure.
 18. The method according to claim 17, wherein the structuralelements include a material selected from the group consisting of aceramic, metal, a plastic and a resin, and combinations thereof, andwherein the mechanical structure includes a material selected from thegroup consisting of silicon, ceramic, sapphire and glass, andcombinations thereof.
 19. The method according to claim 11, wherein theisolated cavity, the device body, the membrane and the piercingstructure are manufactured using a 3-d printing technique.
 20. Themethod according to claim 19, wherein the 3-d printing technique isselected from the group consisting of stereolithography, polyjet, inkjetprinting, plastic laser sintering, direct metal laser sintering, fuseddeposition modeling, and combinations thereof.